Recent results on aqueous electrolyte cells

NASA Astrophysics Data System (ADS)

Wessells, Colin; Huggins, Robert A.; Cui, Yi

2011-03-01

The improved safety of aqueous electrolytes makes aqueous lithium-ion batteries an attractive alternative to commercial cells utilizing flammable and expensive organic electrolytes. Two important issues relating to their use have been addressed in this work. One is the extension of the usable voltage range by the incorporation of lithium salts, and the other is the investigation of a useful negative electrode reactant, LiTi2(PO4)3. The electrochemical stability of aqueous lithium salt solutions containing two lithium salts, LiNO3 and Li2SO4, has been characterized using a constant current technique. In both cases, concentrated solutions had effective electrolyte stability windows substantially greater than that of pure water under standard conditions. At an electrolyte leakage current of 10 μA cm-2 between two platinum electrodes in 5 M LiNO3 the cell voltage can reach 2.0 V, whereas with a leakage current of 50 μA cm-2 it can reach 2.3 V. LiTi2(PO4)3 was synthesized using a Pechini method and cycled in pH-neutral Li2SO4. At a reaction potential near the lower limit of electrolyte stability, an initial discharge capacity of 118 mAh g-1 was measured at a C/5 rate, while about 90% of this discharge capacity was retained after 100 cycles. This work demonstrates that it is possible to have useful aqueous electrolyte lithium-ion batteries using the LiTi2(PO4)3 anode with cell voltages of 2 V and above.

ELECTROCHEMICAL DECONTAMINATION AND RECOVERY OF URANIUM VALUES

DOEpatents

McLaren, J.A.; Goode, J.H.

1958-05-13

An electrochemical process is described for separating uranium from fission products. The method comprises subjecting the mass of uranium to anodic dissolution in an electrolytic cell containing aqueous alkali bicarbonate solution as its electrolyte, thereby promoting a settling from the solution of a solid sludge from about the electrodes and separating the resulting electrolyte solution containing the anodically dissolved uranium from the sludge which contains the rare earth fission products.

Thermodynamic characteristics of protolytic equilibria of L-serine in aqueous solutions

NASA Astrophysics Data System (ADS)

Kochergina, L. A.; Volkov, A. V.; Khokhlova, E. A.; Krutova, O. N.

2011-05-01

The heat effects of the reaction of aqueous solution of L-serine with aqueous solutions of HNO3 and KOH were determined by calorimetry at temperatures of 288.15, 298.15, and 308.15 K, and ionic strength values of 0.2, 0.5, and 1.0 (background electrolyte, KNO3). Standard thermodynamic characteristics (Δr H o, Δr G o, Δr S o, Δ C {/p o}) of the acid-base reactions in aqueous solutions of L-serine were calculated. The effect of the concentration of background electrolyte and temperature on the heats of dissociation of amino acid was considered. The combustion energy of L-serine by bomb calorimetry in the medium of oxygen was determined. The standard combustion and formation enthalpies of crystalline L-serine were calculated. The heats of dissolution of crystalline L-serine in water and solutions of potassium hydroxide at 298.15 K were measured by direct calorimetry. The standard enthalpies of formation of L-serine and products of its dissociation in aqueous solution were calculated.

Modifications in structure and interaction of nanoparticle-protein-surfactant complexes in electrolyte solution

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Kumar, S.; Aswal, V. K.; Schweins, R.

2016-05-01

SANS experiments of three-component system of anionic silica nanoparticles, anionic BSA protein and anionic SDS surfactants have been carried out without and with electrolyte in aqueous solution. In both the cases, the interaction of surfactant with protein results in formation of bead-necklace structure of protein-surfactant complexes in solution. These protein-surfactant complexes interact very differently with nanoparticles in absence and presence of electrolyte. In absence of electrolyte, nanoparticles remain in dispersed phase in solution, whereas with the addition of electrolyte the nanoparticles fractal aggregates are formed. SANS describes the phase behavior to be governed by competition of electrostatic and depletion interactions among the components solution.

A concentrated electrolyte for zinc hexacyanoferrate electrodes in aqueous rechargeable zinc-ion batteries

NASA Astrophysics Data System (ADS)

Kim, D.; Lee, C.; Jeong, S.

2018-01-01

In this study, a concentrated electrolyte was applied in an aqueous rechargeable zinc-ion battery system with a zinc hexacyanoferrate (ZnHCF) electrode to improve the electrochemical performance by changing the hydration number of the zinc ions. To optimize the active material, ZnHCF was synthesized using aqueous solutions of zinc nitrate with three different concentrations. The synthesized materials exhibited some differences in structure, crystallinity, and particle size, as observed by X-ray diffraction and scanning electron microscopy. Subsequently, these well-structured materials were applied in electrochemical tests. A more than two-fold improvement in the charge/discharge capacities was observed when the concentrated electrolyte was used instead of the dilute electrolyte. Additionally, the cycling performance observed in the concentrated electrolyte was superior to that in the dilute electrolyte. This improvement in the electrochemical performance may result from a decrease in the hydration number of the zinc ions in the concentrated electrolyte.

Unusual effect of the magnetic field component of the microwave radiation on aqueous electrolyte solutions.

PubMed

Horikoshi, Satoshi; Sumi, Takuya; Serpone, Nick

2012-01-01

The heating characteristics of aqueous electrolyte solutions (NaCl, KCl, CaCl2, NaBF4, and NaBr) of varying concentrations in ultrapure water by 2.45 GHz microwave radiation from a single-mode resonance microwave device and a semiconductor microwave generator were examined under conditions where the electric field (E-field) was dominant and where the magnetic field (H-field) dominated. Although magnetic field heating is not generally used in microwave chemistry, the electrolyte solutions were heated almost entirely by the microwaves' H-field. The heating rates under H-field irradiation at the higher concentrations of electrolytes (0.125 M to 0.50 M) exceeded the rates under E-field irradiation. This inversion phenomenon in heating is described in terms of the penetration depth of the microwaves. On the other hand, the action of the microwave radiation on ethylene glycol containing an electrolyte differed from that observed for water under E-field and H-field conditions.

The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration.

PubMed

Smith, Alexander M; Lee, Alpha A; Perkin, Susan

2016-06-16

According to classical electrolyte theories interactions in dilute (low ion density) electrolytes decay exponentially with distance, with the Debye screening length the characteristic length scale. This decay length decreases monotonically with increasing ion concentration due to effective screening of charges over short distances. Thus, within the Debye model no long-range forces are expected in concentrated electrolytes. Here we reveal, using experimental detection of the interaction between two planar charged surfaces across a wide range of electrolytes, that beyond the dilute (Debye-Hückel) regime the screening length increases with increasing concentration. The screening lengths for all electrolytes studied-including aqueous NaCl solutions, ionic liquids diluted with propylene carbonate, and pure ionic liquids-collapse onto a single curve when scaled by the dielectric constant. This nonmonotonic variation of the screening length with concentration, and its generality across ionic liquids and aqueous salt solutions, demonstrates an important characteristic of concentrated electrolytes of substantial relevance from biology to energy storage.

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments.

PubMed

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert; Bradforth, Stephen E; Schwegler, Eric; Galli, Giulia

2017-06-01

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

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

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecularmore » dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.« less

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

Potential of Zero Charge and Its Temperature Derivative for Au(111) Electrode|Alkanethiol SAM|1.0 M Aqueous Electrolyte Solution Interfaces: Impact of Electrolyte Solution Ionic Strength and Its Effect on the Structure of the Modified Electrode|Electrolyte Solution Interface

DOE PAGES

Smalley, John F.

2017-04-06

In this study, we demonstrate how small and rapid temperature perturbations (produced by the indirect laser-induced temperature jump (ILIT) technique) of solid metal electrode|electrolyte solution interfaces may be used to determine the potential of zero (total) charge (E pzc) and its temperature derivativemore » $$\\left(\\frac{dEpzc}{dT}\\right)$$ of Au(111) electrode surfaces modified by alkanethiol self-assembled monolayers in contact with high ionic strength (i.e., 1.0 M) aqueous electrolyte solutions. The E pzc’s measured for two different types of SAMs (made from either HS(CH 2) n-1CH 3 (5 ≤ n ≤ 12, E pzc = -(0.99 ± 0.12) V vs SSCE) or HS(CH 2) nOH (3 ≤ n ≤ 16, E pzc = (0.46 ± 0.22) V vs SSCE)) are considerably different than those measured previously at much lower electrolyte solution ionic strengths. For mixed monolayers made from both HS(CH 2) n-1CH 3 and HS(CH 2) nFc (where Fc refers to ferrocene), the difference in Epzc decreases as a function of the surface concentration of the Fc moiety (i.e., [Fc]), and it completely disappears at a surprisingly small [Fc] (~4.0 × 10 –11 mol cm –2). These observations for the Au(111)|hydrophobic (neat and mixed) SAM|aqueous electrolyte solution interfaces, along with the surface potentials (g Sml(dip)) evaluated for the contacting electrolyte solution surfaces of these interfaces, are consistent with a structure for the water molecule components of these surfaces where there is a net orientation of the dipoles of these molecules. Accordingly, the negative (oxygen) ends of these molecules point toward the SAM surface. The positive values of g Sml(dip) evaluated for hydrophilic SAM (e.g., made from HS(CH 2) nOH)|aqueous electrolyte solution interfaces) also indicate that the structure of these interfaces is similar to that of the hydrophobic interfaces. However, g Sml(dip) decreases with increasing ionic strength for the hydrophilic interfaces, while it increases with increasing ionic strength for the hydrophobic interfaces. The data (and calculations) reported in the present work and other studies of hydrophobic (and hydrophilic)|aqueous solution interfaces are as yet insufficient to support a complete explanation for the effects of ionic strength observed in the present study. Nevertheless, an analysis based upon the value of $$\\left(\\frac{dEpzc}{dT}\\right)$$ (= (0.51 ± 0.12) mV/K, essentially the same for SAMs made from both HS(CH 2) n-1CH 3 and HS(CH 2) nOH), determined in the present study provides a further indication that upon formation of the SAM there is a partial charge transfer of electrons from the relevant gold atoms on the Au(111) surface to the sulfur atoms of the alkanethiols.« less

Thermodynamic properties of potassium chloride aqueous solutions

NASA Astrophysics Data System (ADS)

Zezin, Denis; Driesner, Thomas

2017-04-01

Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

Control Of Screening Of A Charged Particle In Electrolytic Aqueous Paul Trap

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

Park, Jae Hyun; Krstic, Predrag S.

2011-06-01

Individual charged particles could be trapped and confined by the combined radio-frequency and DC quadrupole electric field of an aqueous Paul trap. Viscosity of water improves confinement and extends the range of the trap parameters which characterize the stability of the trap. Electrolyte, if present in aqueous solution, may screen the charged particle and thus partially or fully suppress electrophoretic interaction with the applied filed, possibly reducing it to a generally much weaker dielectrophoretic interaction with an induced dipole. Applying molecular dynamics simulation we show that the quadrupole field has a different effect at the electrolyte ions and at muchmore » heavier charged particle, effectively eliminating the screening by electrolyte ions and reinstating the electrophoretic confinement.« less

Measurement of Surface Forces

DTIC Science & Technology

1990-11-16

creating an electrical double-layer whenever a bare mica surface is in contact with an aqueous solution . The mica/electrolyte double-layer...between mica in aqueous solutions containing 10-5 to I M KNO 3 (From Reference 44. Copyright 0 1985 Royal Swedish Academy. Reprinted with permission of...can be observed in aqueous KNO 3 solutions at close separations and at high ion concentrations. For example, if the force curves in Figure 8 (top) for

Separations by supported liquid membrane cascades

DOEpatents

Danesi, Pier R.

1986-01-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid membranes. The membranes contain alternatively a liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solutions and the supported liquid membranes are arranged in such a way to provide a continuous process which leads to the continuous enrichment of the species which show the highest permeability coefficients. By virtue of the very high number of stages which can be arranged, even chemical species having very similar chemical behavior (and consequently very similar permeability coefficients) can be completely separated. The invention also provide a way to concentrate the separated species.

Excluded volume and ion-ion correlation effects on the ionic atmosphere around B-DNA: Theory, simulations, and experiments

PubMed Central

Ovanesyan, Zaven; Fenley, Marcia O.; Guerrero-García, Guillermo Iván; Olvera de la Cruz, Mónica

2014-01-01

The ionic atmosphere around a nucleic acid regulates its stability in aqueous salt solutions. One major source of complexity in biological activities involving nucleic acids arises from the strong influence of the surrounding ions and water molecules on their structural and thermodynamic properties. Here, we implement a classical density functional theory for cylindrical polyelectrolytes embedded in aqueous electrolytes containing explicit (neutral hard sphere) water molecules at experimental solvent concentrations. Our approach allows us to include ion correlations as well as solvent and ion excluded volume effects for studying the structural and thermodynamic properties of highly charged cylindrical polyelectrolytes. Several models of size and charge asymmetric mixtures of aqueous electrolytes at physiological concentrations are studied. Our results are in good agreement with Monte Carlo simulations. Our numerical calculations display significant differences in the ion density profiles for the different aqueous electrolyte models studied. However, similar results regarding the excess number of ions adsorbed to the B-DNA molecule are predicted by our theoretical approach for different aqueous electrolyte models. These findings suggest that ion counting experimental data should not be used alone to validate the performance of aqueous DNA-electrolyte models. PMID:25494770

Liquid electrode

DOEpatents

Ekechukwu, Amy A.

1994-01-01

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

Predicting the electronic properties of aqueous solutions from first-principles

NASA Astrophysics Data System (ADS)

Schwegler, Eric; Pham, Tuan Anh; Govoni, Marco; Seidel, Robert; Bradforth, Stephen; Galli, Giulia

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum-mechanical methods. Yet it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. Here we propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, based on the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results for the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of their electronic properties, including excitation energies, of the solvent and solutes. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies. Part of this work was performed under the auspices of the U.S. Department of Energy at LLNL under Contract DE-AC52-07A27344.

Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Lee, Kuang-Tsin; Wu, Nae-Lih

An aqueous gel electrolyte has for the first time been successfully applied to the MnO 2· nH 2O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H 2O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10 -1 S cm -1. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg).

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

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

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

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

DOEpatents

Spiegel, Ella F.; Sammells, Anthony F.

2001-01-01

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

ELECTROLYTIC SOLUTIONS. Annual Progress Report, May 1, 1962-June 1, 1963

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

Braunstein, J.

Results of investigations of the thermodynamics of association in molten salts and in concentrated aqueous electrolyte solutions are reported. Association constants of Pb(II) with chloride or bromide and of Cd(II) with chloride or bromide in molten mixtures of LiNC/sub 3/ and KNO/sub 3/ were measured potentiometrically at several temperatures and compared with previous results in mixtures of NaNO/sub 3/ and KNO/sub 3/. The anomalous'' solvent effect of lithium ion, reported previously for the association of Cd(II) with bromide was observed aiso for the other associations and a tentative explanation is suggested. The temperature dependence of the association constants was foundmore » to be in agreement with the quasi-lattice model. The association constant of Ag(I) with iodide in molten mixtures of NaNO/sub 3/ and KNO/sub 3/ was measured and compared with previous results in pure KNO/sub 3/. The solvent effect was consistent with the reciprocal coulomb effect.'' Techniques were developed, and preliminary results obtained for measuring association constants in the solvent system KNO/sub 3/--Ca(NO/sub 3/)/sub 2/ in order to investigate the effect of charge as well as size of solvent cation on association constants in molten salt solutions. The measurement of association constants in concentrated aqueous electrolyte solutions was continued. The association of Cd(II) with bromide in aqueous LiNC/sub 3/ was measured as part of a program to find a system that would lend itself to investigation over the range between anhydrous molten salt and aqueous electrolyte solution. Cells and electrodes were developed for investigating association constants in equimolar LiNO/sub 3/ -KNO/sub 3/ with controlled small water contents, and preliminary results are reported. (auth)« less

Isotherm-Based Thermodynamic Model for Solute Activities of Asymmetric Electrolyte Aqueous Solutions.

PubMed

Nandy, Lucy; Dutcher, Cari S

2017-09-21

Adsorption isotherm-based statistical thermodynamic models can be used to determine solute concentration and solute and solvent activities in aqueous solutions. Recently, the number of adjustable parameters in the isotherm model of Dutcher et al. J. Phys. Chem. A/C 2011, 2012, 2013 were reduced for neutral solutes as well as symmetric 1:1 electrolytes by using a Coulombic model to describe the solute-solvent energy interactions (Ohm et al. J. Phys. Chem. A 2015, Nandy et al. J. Phys. Chem. A 2016). Here, the Coulombic treatment for symmetric electrolytes is extended to establish improved isotherm model equations for asymmetric 1-2 and 1-3 electrolyte systems. The Coulombic model developed here results in prediction of activities and other thermodynamic properties in multicomponent systems containing ions of arbitrary charge. The model is found to accurately calculate the osmotic coefficient over the entire solute concentration range with two model parameters, related to intermolecular solute-solute and solute-solvent spacing. The inorganic salts and acids treated here are generally considered to be fully dissociated. However, there are certain weak acids that do not dissociate completely, such as the bisulfate ion. In this work, partial dissociation of the bisulfate ion from sulfuric acid is treated as a mixture, with an additional model parameter that accounts for the dissociation ratio of the dissociated ions to nondissociated ions.

Liquid electrode

DOEpatents

Ekechukwu, A.A.

1994-07-05

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

Non-Ideality in Solvent Extraction Systems: PNNL FY 2014 Status Report

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

Levitskaia, Tatiana G.; Chatterjee, Sayandev; Pence, Natasha K.

The overall objective of this project is to develop predictive modeling capabilities for advanced fuel cycle separation processes by gaining a fundamental quantitative understanding of non-ideality effects and speciation in relevant aqueous and organic solutions. Aqueous solutions containing actinides and lanthanides encountered during nuclear fuel reprocessing have high ionic strength and do not behave as ideal solutions. Activity coefficients must be calculated to take into account the deviation from ideality and predict their behavior. In FY 2012-2013, a convenient method for determining activity effects in aqueous electrolyte solutions was developed. Our initial experiments demonstrated that water activity and osmotic coefficientsmore » of the electrolyte solutions can be accurately measured by the combination of two techniques, a Water Activity Meter and Vapor Pressure Osmometry (VPO). The water activity measurements have been conducted for binary lanthanide solutions in wide concentration range for all lanthanides (La-Lu with the exception of Pm). The osmotic coefficients and Pitzer parameters for each binary system were obtained by the least squares fitting of the water activity data. However, application of Pitzer model for the quantitative evaluation of the activity effects in the multicomponent mixtures is difficult due to the large number of the required interaction parameters. In FY 2014, the applicability of the Bromley model for the determination of the Ln(NO 3) 3 activity coefficients was evaluated. The new Bromley parameters for the binary Ln(NO 3) 3 electrolytes were obtained based on the available literature and our experimental data. This allowed for the accurate prediction of the Ln(NO 3) 3 activity coefficients for the binary Ln(NO 3) 3 electrolytes. This model was then successfully implemented for the determination of the Ln(NO 3) 3 activity coefficients in the ternary Nd(NO 3) 3/HNO 3/H2O, Eu(NO 3) 3/HNO 3/H 2O, and Eu(NO 3) 3/NaNO 3/H 2O systems. The main achievement of this work is the verified pathway for the estimation of the activity coefficients in the multicomponent aqueous electrolyte systems. The accurate Bromley electrolytes contributions obtained in this work for the entire series of lanthanide(III) nitrates (except Pm) can be applied for predicting activity coefficients and non-ideality effects for multi-component systems containing these species. This work also provides the proof-of-principle of extending the model to more complex multicomponent systems. Moreover, this approach can also be applied to actinide-containing electrolyte systems, for determination of the activity coefficients in concentrated radioactive solutions.« less

Liquid junction schottky barrier solar cell

DOEpatents

Williams, Richard

1980-01-01

A mixture of ceric ions (Ce.sup.+4) and cerous ions (Ce.sup.+3) in an aqueous electrolyte solution forms a Schottky barrier at the interface between an active region of silicon and the electrolyte solution. The barrier height obtained for hydrogenated amorphous silicon using the Ce.sup.+4 /Ce.sup.+3 redox couple is about 1.7 eV.

A study on lithium/air secondary batteries-Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions

NASA Astrophysics Data System (ADS)

Shimonishi, Yuta; Zhang, Tao; Imanishi, Nobuyuki; Im, Dongmin; Lee, Dong Joon; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu; Sammes, Nigel

The stability of the high lithium ion conducting glass ceramics, Li 1+ x+ yTi 2- xAl xSi yP 3- yO 12 (LTAP) in alkaline aqueous solutions with and without LiCl has been examined. A significant conductivity decrease of the LTAP plate immersed in 0.057 M LiOH aqueous solution at 50 °C for 3 weeks was observed. However, no conductivity change of the LTAP plate immersed in LiCl saturated LiOH aqueous solutions at 50 °C for 3 weeks was observed. The pH value of the LiCl-LiOH-H 2O solution with saturated LiCl was in a range of 7-9. The molarity of LiOH and LiCl in the LiOH and LiCl saturated aqueous solution were estimated to be 5.12 and 11.57 M, respectively, by analysis of Li + and OH -. The high concentration of LiOH and the low pH value of 8.14 in this solution suggested that the dissociation of LiOH into Li + and OH - is too low in the solution with a high concentration of Li +. These results suggest that the water stable LTAP could be used as a protect layer of the lithium metal anode in the lithium/air cell with LiCl saturated aqueous solution as the electrolyte, because the content of OH - ions in the LiCl saturated aqueous solution does not increase via the cell reaction of Li + 1/2O 2 + H 2O → 2LiOH, and LTAP is stable under a deep discharge state.

Effect of the additives on clouding behavior and thermodynamics of coenzyme Q10-Kolliphor HS15 micelle aqueous solutions

NASA Astrophysics Data System (ADS)

Hu, Li; Zhang, Jing; Zhu, Chao; Pan, Hong-chun; Liu, Hong

2017-11-01

Herein we investigate the effect of different additives (electrolytes, amino acids, PEG, and sugars) on the cloud points (CP) of coenzyme Q10 (CoQ10) - Kolliphor HS15 (HS15) micelle aqueous solutions. The CP values were decreased with the increase of electrolytes and sugars, following: CPAl3+ < CPMg2+ < CPCa2+ < CPNa+ < CPK+ < CPNH4+; CPdisaccharide < CPmonosaccharide. The presences of Arginine and Tryptophan significantly increased the CP; while the other amino acids reduced the CP. A depression of CP for CoQ10-HS15 micelle solution with PEG was molecular weight of PEG dependent. The significant thermodynamic parameters were also evaluated and discussed.

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

Jeffries-Nakamura, Barbara (Inventor); Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Valdez, Thomas I. (Inventor)

2006-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

2002-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Control of Screening of a Charged Particle in Electrolytic Aqueous Paul Trap

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

Park, Jae Hyun nmn; Krstic, Predrag S

2011-01-01

Individual charged particles could be trapped and confined in the combined radio-frequency and DC quadrupole electric field of an aqueous Paul trap. Viscosity of water improves confinement and extends the range of the trap parameters which characterize the stability of the trap. Electrolyte, if present in aqueous solution, may screen the charged particle and thus partially or fully suppress electrophoretic interaction with the applied filed, possibly reducing it to a generally much weaker dielectrophoretic interaction with an induced dipole. Applying molecular dynamics simulation we show that the quadrupole field has a different affects at the electrolyte ions and at muchmore » heavier charged particle, effectively eliminating the screening effect and reinstating the electrophoretic confinement.« less

First-principles molecular dynamics simulation study on electrolytes for use in redox flow battery

NASA Astrophysics Data System (ADS)

Choe, Yoong-Kee; Tsuchida, Eiji; Tokuda, Kazuya; Ootsuka, Jun; Saito, Yoshihiro; Masuno, Atsunobu; Inoue, Hiroyuki

2017-11-01

Results of first-principles molecular dynamics simulations carried out to investigate structural aspects of electrolytes for use in a redox flow battery are reported. The electrolytes studied here are aqueous sulfuric acid solutions where its property is of importance for dissolving redox couples in redox flow battery. The simulation results indicate that structural features of the acid solutions depend on the concentration of sulfuric acid. Such dependency arises from increase of proton dissociation from sulfuric acid.

Surface-charge-governed electrolyte transport in carbon nanotubes

NASA Astrophysics Data System (ADS)

Xue, Jian-Ming; Guo, Peng; Sheng, Qian

2015-08-01

The transport behavior of pressure-driven aqueous electrolyte solution through charged carbon nanotubes (CNTs) is studied by using molecular dynamics simulations. The results reveal that the presence of charges around the nanotube can remarkably reduce the flow velocity as well as the slip length of the aqueous solution, and the decreasing of magnitude depends on the number of surface charges and distribution. With 1-M KCl solution inside the carbon nanotube, the slip length decreases from 110 nm to only 14 nm when the number of surface charges increases from 0 to 12 e. This phenomenon is attributed to the increase of the solid-liquid friction force due to the electrostatic interaction between the charges and the electrolyte particles, which can impede the transports of water molecules and electrolyte ions. With the simulation results, we estimate the energy conversion efficiency of nanofluidic battery based on CNTs, and find that the highest efficiency is only around 30% but not 60% as expected in previous work. Project supported by the National Natural Science Foundation of China (Grant Nos. 11375031 and 11335003).

Sustainable Carbon/Carbon Supercapacitors Operating Down to -40 °C in Aqueous Electrolyte Made with Cholinium Salt.

PubMed

Abbas, Qamar; Béguin, François

2018-03-09

Cholinium chloride at a concentration of 5 mol kg -1 in water is proposed as a low-cost and environmentally friendly aqueous electrolyte, enabling extension of the operating range of carbon/carbon supercapacitors (SCs) down to -40 °C. This solution has a pH close to neutrality (pH 6.1) and high conductivity of 88 mS cm -1 at 24 °C. The supercapacitors demonstrate a high capacitance of 126 F g -1 (per mass of one electrode) and long life span at voltages up to 1.5 V. At -40 °C, the carbon/carbon SCs display excellent electrochemical characteristics with only slightly reduced capacitance of 106 F g -1 and negligible ohmic losses. As compared to previous works, where antifreezing additives were introduced in traditional neutral electrolytes, the low solubility of the salt and related poor conductivity of the solution is no longer an issue, which makes cholinium salt aqueous solutions very promising for SCs operating at sub-ambient temperature conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-aqueous solution preparation of doped and undoped lixmnyoz

DOEpatents

Boyle, Timothy J.; Voigt, James A.

1997-01-01

A method for generation of phase-pure doped and undoped Li.sub.x Mn.sub.y O.sub.z precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder.

Molecular simulations of diffusion in electrolytes

NASA Astrophysics Data System (ADS)

Wheeler, Dean Richard

This work demonstrates new methodologies for simulating multicomponent diffusion in concentrated solutions using molecular dynamics (MD). Experimental diffusion data for concentrated multicomponent solutions are often lacking, as are accurate methods of predicting diffusion for nonideal solutions. MD can be a viable means of understanding and predicting multicomponent diffusion. While there have been several prior reports of MD simulations of mutual diffusion, no satisfactory expressions for simulating Stefan-Maxwell diffusivities for an arbitrary number of species exist. The approaches developed here allow for the computation of a full diffusion matrix for any number of species in both nonequilibrium and equilibrium MD ensembles. Our nonequilibrium approach is based on the application of constant external fields to drive species diffusion. Our equilibrium approach uses a newly developed Green-Kubo formula for Stefan-Maxwell diffusivities. In addition, as part of this work, we demonstrate a widely applicable means of increasing the computational efficiency of the Ewald sum, a technique for handling long-range Coulombic interactions in simulations. The theoretical development is applicable to any solution which can be simulated using MD; nevertheless, our primary interest is in electrochemical applications. To this end, the methods are tested by simulations of aqueous salt solutions and lithium-battery electrolytes. KCl and NaCl aqueous solutions were simulated over the concentration range 1 to 4 molal. Intermolecular-potential models were parameterized for these transport-based simulations. This work is the first to simulate all three independent diffusion coefficients for aqueous NaCl and KCl solutions. The results show that the nonequilibrium and equilibrium methods are consistent with each other, and in moderate agreement with experiment. We simulate lithium-battery electrolytes containing LiPF6 in propylene carbonate and mixed ethylene carbonate-dimethyl carbonate solvents. As with the aqueous-solution work, potential parameters were generated for these molecules. These nonaqueous electrolytes demonstrate rich transport behavior, which the simulations are able to reproduce qualitatively. In a mixed-solvent simulation we regress all six independent transport coefficients. The simulations show that strong ion pairing is responsible for the increase in viscosity and maximum in conductivity as ion concentrations are increased.

Surface layer formation of LiCoO2 thin film electrodes in non-aqueous electrolyte containing lithium bis(oxalate)borate

NASA Astrophysics Data System (ADS)

Matsui, Masaki; Dokko, Kaoru; Akita, Yasuhiro; Munakata, Hirokazu; Kanamura, Kiyoshi

2012-07-01

Surface layer formation processes on a LiCoO2 thin film electrode in a non-aqueous electrolyte containing lithium bis(oxalate)borate (LiBOB) were investigated using in situ FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The in situ FTIR spectra of the electrolyte solution containing LiBOB showed that the adsorption of BOB anions on the electrode surface occurred during the charge process of the LiCoO2 thin film electrode above 4.0 V. XPS analysis for the LiCoO2 thin film electrode charged in an electrolyte containing LiBOB suggested that the adsorbed BOB anions on the electrode surface prevent the continuous decomposition of hexafluorophosphate (PF6) anions resulting in the formation of a very thin surface layer containing organic species, while the LiCoO2 charged in a LiPF6 solution had a relatively thick surface layer containing organic species and inorganic species.

A new method for multicomponent activity coefficients of electrolytes in aqueous atmospheric aerosols

NASA Astrophysics Data System (ADS)

Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

2005-01-01

Three-dimensional models of atmospheric inorganic aerosols need accurate and computationally efficient parameterizations of activity coefficients of various electrolytes in multicomponent aqueous solutions. In this paper, we extend the Taylor's series expansion mixing rule used by C. Wagner in 1952 for estimating activity coefficients in dilute alloy solutions to aqueous electrolyte solutions at any concentration. The resulting method, called the multicomponent Taylor expansion method (MTEM), estimates the mean activity coefficient of an electrolyte in a multicomponent solution on the basis of its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. MTEM is applied here for atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+, SO42-, HSO4-, NO3-, and Cl- ions. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson (ZSR) method. For self-consistency, most of the MTEM and ZSR parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K and are valid for an aw range of 0.2-0.97. Because CaSO4 is sparingly soluble, it is treated as a solid in the model over the entire aw range. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols and is contrasted against the mixing rule of C. L. Kusik and H. P. Meissner and of L. A. Bromley and the newer approach of S. Metzger and colleagues. Predictions of MTEM are found to be generally within a factor of 0.8-1.25 of the comprehensive Pitzer-Simonson-Clegg model and are shown to be significantly more accurate than predictions of the other three methods. MTEM also yields a noniterative solution of the bisulfate ion dissociation in sulfate-rich systems: a major computational advantage over other ionic-strength-based methods that require an iterative solution. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.

Process for electrolytic deposition of metals on zirconium materials

DOEpatents

Donaghy, Robert E.

1979-01-30

A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors.

PubMed

Wu, Zhong-Shuai; Ren, Wencai; Wang, Da-Wei; Li, Feng; Liu, Bilu; Cheng, Hui-Ming

2010-10-26

In order to achieve high energy and power densities, we developed a high-voltage asymmetric electrochemical capacitor (EC) based on graphene as negative electrode and a MnO(2) nanowire/graphene composite (MGC) as positive electrode in a neutral aqueous Na(2)SO(4) solution as electrolyte. MGC was prepared by solution-phase assembly of graphene sheets and α-MnO(2) nanowires. Such aqueous electrolyte-based asymmetric ECs can be cycled reversibly in the high-voltage region of 0-2.0 V and exhibit a superior energy density of 30.4 Wh kg(-1), which is much higher than those of symmetric ECs based on graphene//graphene (2.8 Wh kg(-1)) and MGC//MGC (5.2 Wh kg(-1)). Moreover, they present a high power density (5000 W kg(-1) at 7.0 Wh kg(-1)) and acceptable cycling performance of ∼79% retention after 1000 cycles. These findings open up the possibility of graphene-based composites for applications in safe aqueous electrolyte-based high-voltage asymmetric ECs with high energy and power densities.

Calculating Permittivity and Dielectric Loss Frequency Spectra for Aqueous Electrolyte Solutions

NASA Astrophysics Data System (ADS)

Odinaev, S.; Makhmadbegov, R. S.

2018-01-01

Analytic expressions for dielectric permittivity factor ɛ1(ω) and dielectric dissipation factor ɛ2(ω) of electrolyte solutions are obtained, based on the ratio between complex factors of dielectric permittivity and specific conductivity. The range of frequency dispersion of dynamic factors ɛ1(ω) and ɛ2(ω) for aqueous solutions of LiCl, NaCl, KCl, and CsCl is considered. Numerical calculations are performed for friction coefficients β a and β b ; relaxation times τ a , τ b , and τ ab ; and factors ɛ1(ω) and ɛ2(ω) in a wide range of variation for ρ; concentration c; temperature T; and frequencies ω. The resulting theoretically calculated ɛ1(ω) and ɛ2(ω) values and the Cole-Cole diagram are in quantitative agreement with experimental data.

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

PubMed

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

2018-02-12

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

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

PubMed Central

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

2018-01-01

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

Studies of Partial Molar Volumes of Some Narcotic-Analgesic Drugs in Aqueous-Alcoholic Mixtures at 25°C

NASA Astrophysics Data System (ADS)

Sharma, Poonam; Chauhan, S.; Syal, V. K.; Chauhan, M. S.

2008-04-01

Partial molar volumes of the drugs Parvon Spas, Parvon Forte, Tramacip, and Parvodex in aqueous mixtures of methanol (MeOH), ethanol (EtOH), and propan-1-ol (1-PrOH) have been determined. The data have been evaluated using the Masson equation. The parameters, apparent molar volumes {(φ_v)}, partial molar volumes {(φ_v0)}, and S v values (experimental slopes) have been interpreted in terms of solute solvent interactions. In addition, these studies have also been extended to determine the effect of these drugs on the solvation behavior of an electrolyte (sodium chloride), a surfactant (sodium dodecyl sulfate), and a non-electrolyte (sucrose). It can be inferred from these studies that all drug cations can be regarded as structure makers/promoters due to hydrophobic hydration. Furthermore, the results are correlated to understand the solution behavior of drugs in aqueous-alcoholic systems, as a function of the nature of the alcohol and solutes.

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.

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

PubMed

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

A bio-inspired molecular water oxidation catalyst for renewable hydrogen generation: an examination of salt effects

NASA Astrophysics Data System (ADS)

Brimblecombe, Robin; Rotstein, Miriam; Koo, Annette; Dismukes, G. Charles; Swiegers, Gerhard F.; Spiccia, Leone

2009-08-01

Most transport fuels are derived from fossil fuels, generate greenhouse gases, and consume significant amounts of water in the extraction, purification, and/or burning processes. The generation of hydrogen using solar energy to split water, ideally from abundant water sources such as sea water or other non-potable sources, could potentially provide an unlimited, clean fuel for the future. Solar, electrochemical water splitting typically combines a photoanode at which water oxidation occurs, with a cathode for proton reduction to hydrogen. In recent work, we have found that a bioinspired tetra-manganese cluster catalyzes water oxidation at relatively low overpotentials (0.38 V) when doped into a Nafion proton conduction membrane deposited on a suitable electrode surface, and illuminated with visible light. We report here that this assembly is active in aqueous and organic electrolyte solutions containing a range of different salts in varying concentrations. Similar photocurrents were obtained using electrolytes containing 0.0 - 0.5 M sodium sulfate, sodium perchlorate or sodium chloride. A slight decline in photocurrent was observed for sodium perchlorate but only at and above 5.0 M concentration. In acetonitrile and acetone solutions containing 10% water, increasing the electrolyte concentration was found to result in leaching of the catalytic species from the membrane and a decrease in photocurrent. Leaching was not observed when the system was tested in an ionic liquid containing water, however, a lower photocurrent was generated than observed in aqueous electrolyte. We conclude that immersion of the membrane in an aqueous solution containing an electrolyte concentration of 0.05 - 0.5M represent good conditions for operation for the cubium/Nafion catalytic system.

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kelly, Jesse C.

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

Method for providing uranium articles with a corrosion resistant anodized coating

DOEpatents

Waldrop, Forrest B.; Washington, Charles A.

1982-01-01

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75.degree. C. with a current flow of less than about 0.036 A/cm.sup.2 of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

Electrolyte additive for improved battery performance

DOEpatents

Bellows, Richard J.; Kantner, Edward

1989-04-04

In one embodiment of the present invention, there is provided an electrochemical cell having a metal bromine couple. The cell includes an electrode structure on which to deposit the metal of the couple and a counterelectrode at which to generate bromine. A microporous membrane separates the electrode and counterelectrode. Importantly, the aqueous electrolyte comprises an aqueous metal bromide solution containing a water soluble bromine complexing agent capable of forming a water immiscible complex with bromine and an additive capable of decreasing the wettability of the microporous separators employed in such cells by such water immiscible bromine complexes.

Non-aqueous solution preparation of doped and undoped Li{sub x}Mn{sub y}O{sub z}

DOEpatents

Boyle, T.J.; Voigt, J.A.

1997-05-20

A method is described for generation of phase-pure doped and undoped Li{sub x}Mn{sub y}O{sub z} precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder. 1 fig.

GEOSURF: a computer program for modeling adsorption on mineral surfaces from aqueous solution

NASA Astrophysics Data System (ADS)

Sahai, Nita; Sverjensky, Dimitri A.

1998-11-01

A new program, GEOSURF, has been developed for calculating aqueous and surface speciation consistent with the triple-layer model of surface complexation. GEOSURF is an extension of the original programs MINEQL, MICROQL and HYDRAQL. We present, here, the basic algorithm of GEOSURF along with a description of the new features implemented. GEOSURF is linked to internally consistent data bases for surface species (SURFK.DAT) and for aqueous species (AQSOL.DAT). SURFK.DAT contains properties of minerals such as site densities, and equilibrium constants for adsorption of aqueous protons and electrolyte ions on a variety of oxides and hydroxides. The Helgeson, Kirkham and Flowers version of the extended Debye-Huckel Equation for 1:1 electrolytes is implemented for calculating aqueous activity coefficients. This permits the calculation of speciation at ionic strengths greater than 0.5 M. The activity of water is computed explicitly from the osmotic coefficient of the solution, and the total amount of electrolyte cation (or anion) is adjusted to satisfy the electroneutrality condition. Finally, the use of standard symbols for chemical species rather than species identification numbers is included to facilitate use of the program. One of the main limitations of GEOSURF is that aqueous and surface speciation can only be calculated at fixed pH and at fixed concentration of total adsorbate. Thus, the program cannot perform reaction-path calculations: it cannot determine whether or not a solution is over- or under-saturated with respect to one or more solid phases. To check the proper running of GEOSURF, we have compared results generated by GEOSURF with those from two other programs, HYDRAQL and EQ3. The Davies equation and the "bdot" equation, respectively, are used in the latter two programs for calculating aqueous activity coefficients. An example of the model fit to experimental data for rutile in 0.001 M-2.0 M NaNO 3 is included.

Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

DOE PAGES

Chialvo, Ariel A.; Vlcek, Lukas

2015-05-22

We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation ofmore » four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.« less

ELECTRODEPOSITION OF PLUTONIUM

DOEpatents

Wolter, F.J.

1957-09-10

A process of electrolytically recovering plutonium from dilute aqueous solutions containing plutonium ions comprises electrolyzing the solution at a current density of about 0.44 ampere per square centimeter in the presence of an acetate-sulfate buffer while maintaining the pH of the solution at substantially 5 and using a stirred mercury cathode.

Anomalously enhanced hydration of aqueous electrolyte solution in hydrophobic carbon nanotubes to maintain stability.

PubMed

Ohba, Tomonori

2014-02-24

An understanding of the structure and behavior of electrolyte solutions in nanoenvironements is crucial not only for a wide variety of applications, but also for the development of physical, chemical, and biological processes. We demonstrate the structure and stability of electrolyte in carbon nanotubes using hybrid reverse Monte Carlo simulations of X-ray diffraction patterns. Hydrogen bonds between water are adequately formed in carbon nanotubes, although some hydrogen bonds are restricted by the interfaces of carbon nanotubes. The hydrogen bonding network of water in electrolyte in the carbon nanotubes is further weakened. On the other hand, formation of the ion hydration shell is significantly enhanced in the electrolyte in the carbon nanotubes in comparison to ion hydration in bulk electrolyte. The significant hydrogen bond and hydration shell formation are a result of gaining stability in the hydrophobic nanoenvironment. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for providing uranium articles with a corrosion-resistant anodized coating

DOEpatents

Waldrop, F.B.; Washington, C.A.

1981-01-07

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75/sup 0/C with a current flow of less than about 0.036 A/cm/sup 2/ of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

Synthesis, characterization and application of doped electrolytic manganese dioxides

NASA Astrophysics Data System (ADS)

Jantscher, Wolfgang; Binder, Leo; Fiedler, Dirk A.; Andreaus, Reinhard; Kordesch, Karl

Electrolytic manganese dioxides (EMDs) were prepared on the 100 g scale by anodic deposition from acidic aqueous solutions of manganese sulfate. In situ doping with titanium ions was achieved by addition of tetra- n-butoxytitanium to the electrolytic bath. Samples were also doped ex situ by washing the products with aqueous barium hydroxide solution. The EMDs were characterized by electron microscopy studies and BET surface area determinations. Cyclic abrasive stripping voltammetry was successfully applied to evaluate the rechargeability of the newly synthesized undoped and doped EMDs in 9 M KOH. Relative discharge capacities at different depths of discharge (DOD) with respect to the first one-electron reduction of γ-MnO 2 are compared for different EMDs. At about 30% DOD, resulting relative discharge capacities show essentially the same trend as those measured in AA cells from about 10 to 20 discharge/charge cycles onwards. Accordingly, titanium-doped EMD was shown to exhibit superior charge retention and rechargeability when compared to the titanium-free samples.

Non-aqueous electrolyte for lithium-ion battery

DOEpatents

Amine, Khalil; Zhang, Lu; Zhang, Zhengcheng

2016-01-26

A substantially non-aqueous electrolyte solution includes an alkali metal salt, a polar aprotic solvent, and an organophosphorus compound of Formula IA, IB, or IC: ##STR00001## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenoxy, alkynoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, siloxyl, silyl, or organophosphatyl; R.sup.5 and R.sup.6 are each independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; R.sup.7 is ##STR00002## and R.sup.8, R.sup.9 and R.sup.10 are each independently alkyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; provided that if the organophosphorus compound is of Formula IB, then at least one of R.sup.5, and R.sup.6 are other than hydrogen, alkyl, or alkenyl; and if the organophosphorus compound is of Formula IC, then the electrolyte solution does not include 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one.

Probing the electrolyte infiltration behaviour of activated carbon supercapacitor electrodes by in situ neutron scattering using aqueous NaCl as electrolyte

DOE PAGES

Liu, Yiqun; Li, Chen; Liu, Cong; ...

2018-04-24

In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.

Probing the electrolyte infiltration behaviour of activated carbon supercapacitor electrodes by in situ neutron scattering using aqueous NaCl as electrolyte

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

Liu, Yiqun; Li, Chen; Liu, Cong

In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.

Gex-Model Using Local Area Fraction for Binary Electrolyte Systems

NASA Astrophysics Data System (ADS)

Haghtalab, Ali; Joda, Marzieh

2007-06-01

The correlation and prediction of phase equilibria of electrolyte systems are essential in the design and operation of many industrial processes such as downstream processing in biotechnology, desalination, hydrometallurgy, etc. In this research, the local composition non-random two liquid-nonrandom factor (NRTL-NRF) model of Haghtalab and Vera was extended for uni-univalent aqueous electrolyte solutions. Based on the assumptions of the NRTL-NRF model, excess Gibbs free energy ( g E) functions were derived for binary electrolyte systems. In this work, the local area fraction was applied and the modified model of NRTL-NRF was developed with either an equal or unequal surface area of an anion to the surface area of a cation. The modified NRTL-NRF models consist of two contributions, one due to long-range forces represented by the Debye-Hückel theory, and the other due to short-range forces, represented by local area fractions of species through nonrandom factors. Each model contains only two adjustable parameters per electrolyte. In addition, the model with unequal surface area of ionic species gives better results in comparison with the second new model with equal surface area of ions. The results for the mean activity coefficients for aqueous solutions of uni-univalent electrolytes at 298.15 K showed that the present model is more accurate than the original NRTL-NRF model.

High-energy-density, aqueous, metal-polyiodide redox flow batteries

DOEpatents

Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

2017-08-29

Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

[Extraction of lambda-cyhalothrin from aqueous dioxan solutions].

PubMed

Shormanov, V K; Chigareva, E N; Belousova, O V

2011-01-01

The results of extraction of lambda-cigalotrin from dioxan aqueous solutions by hydrophobic organic solvents are presented. It is shown that the degree of extraction depends on the nature of the extractant, the water to dioxan ratio, and saturation of the water-dioxan layer with the electrolyte. The highest efficiency of lambda-cigalotrin extraction was achieved using chlorophorm as a solvent under desalination conditions. The extraction factor was calculated necessary to obtain the desired amount of lambda-cigalotrin from the water-dioxan solution (4:1) with the help of the extractants being used.

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

Smalley, John F.

In this study, we demonstrate how small and rapid temperature perturbations (produced by the indirect laser-induced temperature jump (ILIT) technique) of solid metal electrode|electrolyte solution interfaces may be used to determine the potential of zero (total) charge (E pzc) and its temperature derivativemore » $$\\left(\\frac{dEpzc}{dT}\\right)$$ of Au(111) electrode surfaces modified by alkanethiol self-assembled monolayers in contact with high ionic strength (i.e., 1.0 M) aqueous electrolyte solutions. The E pzc’s measured for two different types of SAMs (made from either HS(CH 2) n-1CH 3 (5 ≤ n ≤ 12, E pzc = -(0.99 ± 0.12) V vs SSCE) or HS(CH 2) nOH (3 ≤ n ≤ 16, E pzc = (0.46 ± 0.22) V vs SSCE)) are considerably different than those measured previously at much lower electrolyte solution ionic strengths. For mixed monolayers made from both HS(CH 2) n-1CH 3 and HS(CH 2) nFc (where Fc refers to ferrocene), the difference in Epzc decreases as a function of the surface concentration of the Fc moiety (i.e., [Fc]), and it completely disappears at a surprisingly small [Fc] (~4.0 × 10 –11 mol cm –2). These observations for the Au(111)|hydrophobic (neat and mixed) SAM|aqueous electrolyte solution interfaces, along with the surface potentials (g Sml(dip)) evaluated for the contacting electrolyte solution surfaces of these interfaces, are consistent with a structure for the water molecule components of these surfaces where there is a net orientation of the dipoles of these molecules. Accordingly, the negative (oxygen) ends of these molecules point toward the SAM surface. The positive values of g Sml(dip) evaluated for hydrophilic SAM (e.g., made from HS(CH 2) nOH)|aqueous electrolyte solution interfaces) also indicate that the structure of these interfaces is similar to that of the hydrophobic interfaces. However, g Sml(dip) decreases with increasing ionic strength for the hydrophilic interfaces, while it increases with increasing ionic strength for the hydrophobic interfaces. The data (and calculations) reported in the present work and other studies of hydrophobic (and hydrophilic)|aqueous solution interfaces are as yet insufficient to support a complete explanation for the effects of ionic strength observed in the present study. Nevertheless, an analysis based upon the value of $$\\left(\\frac{dEpzc}{dT}\\right)$$ (= (0.51 ± 0.12) mV/K, essentially the same for SAMs made from both HS(CH 2) n-1CH 3 and HS(CH 2) nOH), determined in the present study provides a further indication that upon formation of the SAM there is a partial charge transfer of electrons from the relevant gold atoms on the Au(111) surface to the sulfur atoms of the alkanethiols.« less

Aluminum as anode for energy storage and conversion: a review

NASA Astrophysics Data System (ADS)

Li, Qingfeng; Bjerrum, Niels J.

Aluminum has long attracted attention as a potential battery anode because of its high theoretical voltage and specific energy. The protective oxide layer on the aluminum surface is however detrimental to the battery performance, contributing to failure to achieve the reversible potential and causing the delayed activation of the anode. By developing aluminum alloys as anodes and solution additives to electrolytes, a variety of aluminum batteries have been extensively investigated for various applications. From molten salt and other non-aqueous electrolytes, aluminum can be electrodeposited and therefore be suitable for developing rechargable batteries. Considerable efforts have been made to develop secondary aluminum batteries of high power density. In the present paper, these research activities are reviewed, including aqueous electrolyte primary batteries, aluminum-air batteries and molten salt secondary batteries.

Unified molecular picture of the surfaces of aqueous acid, base, and salt solutions.

PubMed

Mucha, Martin; Frigato, Tomaso; Levering, Lori M; Allen, Heather C; Tobias, Douglas J; Dang, Liem X; Jungwirth, Pavel

2005-04-28

The molecular structure of the interfacial regions of aqueous electrolytes is poorly understood, despite its crucial importance in many biological, technological, and atmospheric processes. A long-term controversy pertains between the standard picture of an ion-free surface layer and the strongly ion specific behavior indicating in many cases significant propensities of simple inorganic ions for the interface. Here, we present a unified and consistent view of the structure of the air/solution interface of aqueous electrolytes containing monovalent inorganic ions. Molecular dynamics calculations show that in salt solutions and bases the positively charged ions, such as alkali cations, are repelled from the interface, whereas the anions, such as halides or hydroxide, exhibit a varying surface propensity, correlated primarily with the ion polarizability and size. The behavior of acids is different due to a significant propensity of hydronium cations for the air/solution interface. Therefore, both cations and anions exhibit enhanced concentrations at the surface and, consequently, these acids (unlike bases and salts) reduce the surface tension of water. The results of the simulations are supported by surface selective nonlinear vibrational spectroscopy, which reveals among other things that the hydronium cations are present at the air/solution interface. The ion specific propensities for the air/solution interface have important implications for a whole range of heterogeneous physical and chemical processes, including atmospheric chemistry of aerosols, corrosion processes, and bubble coalescence.

Sub-0.5 V Highly Stable Aqueous Salt Gated Metal Oxide Electronics

PubMed Central

Park, Sungjun; Lee, SeYeong; Kim, Chang-Hyun; Lee, Ilseop; Lee, Won-June; Kim, Sohee; Lee, Byung-Geun; Jang, Jae-Hyung; Yoon, Myung-Han

2015-01-01

Recently, growing interest in implantable bionics and biochemical sensors spurred the research for developing non-conventional electronics with excellent device characteristics at low operation voltages and prolonged device stability under physiological conditions. Herein, we report high-performance aqueous electrolyte-gated thin-film transistors using a sol-gel amorphous metal oxide semiconductor and aqueous electrolyte dielectrics based on small ionic salts. The proper selection of channel material (i.e., indium-gallium-zinc-oxide) and precautious passivation of non-channel areas enabled the development of simple but highly stable metal oxide transistors manifested by low operation voltages within 0.5 V, high transconductance of ~1.0 mS, large current on-off ratios over 107, and fast inverter responses up to several hundred hertz without device degradation even in physiologically-relevant ionic solutions. In conjunction with excellent transistor characteristics, investigation of the electrochemical nature of the metal oxide-electrolyte interface may contribute to the development of a viable bio-electronic platform directly interfacing with biological entities in vivo. PMID:26271456

Effects of Temperature on Aggregation Kinetics of Graphene Oxide in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Wang, M.; Gao, B.; Tang, D.; Sun, H.; Yin, X.; Yu, C.

2017-12-01

Temperature may play an important role in controlling graphene oxide (GO) stability in aqueous solutions, but it has been overlooked in the literature. In this work, laboratory experiments were conducted to determine the effects of temperature (6, 25, and 40 °C) on GO aggregation kinetics under different combinations of ionic strength, cation type, humic acid (HA) concentration by monitoring GO hydrodynamic radii and attachment efficiencies. The results showed that, without HA, temperature increase promoted GO aggregation in both monovalent (Na+ and K+) and divalent (Ca2+) solutions. This phenomenon might be caused by multiple processes including enhanced collision frequency, enhanced cation dehydration, and reduced electrostatic repulsion. The presence of HA introduced steric repulsion forces that enhanced GO stability and temperature showed different effects GO aggregation kinetics in monovalent and divalent electrolytes. In monovalent electrolytes, cold temperature diminished the steric repulsion of HA-coated GO. As a result, the fastest increasing rate of GO hydrodynamic radius and the smallest critical coagulation concentration value appeared at the lowest temperature (6 °C). Conversely, in divalent electrolyte solutions with HA, high temperate favored GO aggregation, probably because the interactions between Ca2+ and HA increased with temperature resulting in lower HA coating on GO. Findings of this work emphasized the importance of temperature as well as solution chemistry on the stability and fate of GO nanoparticles in aquatic environment.

Surface and capillary forces encountered by zinc sulfide microspheres in aqueous electrolyte.

PubMed

Gillies, Graeme; Kappl, Michael; Butt, Hans-Jürgen

2005-06-21

The colloid probe technique was used to investigate the interactions between individual zinc sulfide (ZnS) microspheres and an air bubble in electrolyte solution. Incorporation of zinc ions into the electrolyte solution overcomes the disproportionate zinc ion dissolution and mimics high-volume-fraction conditions common in flotation. Determined interaction forces revealed a distinct lack of long-ranged hydrophobic forces, indicated by the presence of a DLVO repulsion prior to particle engulfment. Single microsphere contact angles were determined from particle-bubble interactions. Contact angles increased with decreasing radii and with surface oxidation. Surface modification by the absorption of copper and subsequently potassium O-ethyldithiocarbonate (KED) reduced repulsive forces and strongly increased contact angles.

Conductivity and electrochemical stability of concentrated aqueous choline chloride solutions

NASA Astrophysics Data System (ADS)

Grishina, E. P.; Kudryakova, N. O.

2017-10-01

The conductivity and electrochemical stability of choline chloride (ChCl) solutions with water contents ranging from 20 to 39 wt % are studied. Exposing ChCl to moist ambient air yields a highly concentrated aqueous solution that, as an electrolyte, exhibits the properties and variations in conductivity with temperature and concentration characteristic of other similar systems. Its electrochemical stability window, determined by cyclic voltammetry, is comparable to that of ChCl-based deep eutectic solvents (DESs). Products of the electrolysis of ChCl‒H2O mixtures seem to be less toxic than those of Reline, Ethaline, and Maline.

Cation-Deficient Spinel ZnMn2O4 Cathode in Zn(CF3SO3)2 Electrolyte for Rechargeable Aqueous Zn-Ion Battery.

PubMed

Zhang, Ning; Cheng, Fangyi; Liu, Yongchang; Zhao, Qing; Lei, Kaixiang; Chen, Chengcheng; Liu, Xiaosong; Chen, Jun

2016-10-05

Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMn 2 O 4 /carbon composite as a new Zn-insertion cathode material in aqueous Zn(CF 3 SO 3 ) 2 electrolyte. In 3 M Zn(CF 3 SO 3 ) 2 solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g -1 and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g -1 . The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and promote the use of cation-defective spinel compounds and trifluoromethanesulfonic electrolyte to develop high-performance rechargeable zinc batteries.

Electrolytic Plasma Processing for Sequential Cleaning and Coating Deposition for Cadmium Plating Replacement

DTIC Science & Technology

2008-08-01

deposit Al coatings or ZnAl alloys from aqueous solution. Unfortunately this proved impossible, producing only Al hydroxides and oxides, which are... deposited by normal aqueous electroplating methods. A great deal of effort was expended on attempts to produce metallic Al alloys , but no satisfactory... process . If an Al -bearing salt were soluble in a non- aqueous fluid that did not need an enclosure, then it might be possible to deposit Al coatings

Adsorption of surfactant ions and binding of their counterions at an air/water interface.

PubMed

Tagashira, Hiroaki; Takata, Youichi; Hyono, Atsushi; Ohshima, Hiroyuki

2009-01-01

An expression for the surface tension of an aqueous mixed solution of surfactants and electrolyte ions in the presence of the common ions was derived from the Helmholtz free energy of an air/water surface. By applying the equation to experimental data for the surface tension, the adsorption constant of surfactant ions onto the air/water interface, the binding constant of counterions on the surfactants, and the surface potential and surface charge density of the interface were estimated. The adsorption constant and binding constant were dependent on the species of surfactant ion and counterion, respectively. Taking account of the dependence of surface potential and surface charge density on the concentration of electrolyte, it was suggested that the addition of electrolyte to the aqueous surfactant solution brings about the decrease in the surface potential, the increase in the surface density of surfactant ions, and consequently, the decrease in the surface tension. Furthermore, it was found that the configurational entropy plays a predominant role for the surface tension, compared to the electrical work.

Surface Modification of the LiFePO4 Cathode for the Aqueous Rechargeable Lithium Ion Battery.

PubMed

Tron, Artur; Jo, Yong Nam; Oh, Si Hyoung; Park, Yeong Don; Mun, Junyoung

2017-04-12

The LiFePO 4 surface is coated with AlF 3 via a simple chemical precipitation for aqueous rechargeable lithium ion batteries (ARLBs). During electrochemical cycling, the unfavorable side reactions between LiFePO 4 and the aqueous electrolyte (1 M Li 2 SO 4 in water) leave a highly resistant passivation film, which causes a deterioration in the electrochemical performance. The coated LiFePO 4 by 1 wt % AlF 3 has a high discharge capacity of 132 mAh g -1 and a highly improved cycle life, which shows 93% capacity retention even after 100 cycles, whereas the pristine LiFePO 4 has a specific capacity of 123 mAh g -1 and a poor capacity retention of 82%. The surface analysis results, which include X-ray photoelectron spectroscopy and transmission electron microscopy results, show that the AlF 3 coating material is highly effective for reducing the detrimental surface passivation by relieving the electrochemical side reactions of the fragile aqueous electrolyte. The AlF 3 coating material has good compatibility with the LiFePO 4 cathode material, which mitigates the surface diffusion obstacles, reduces the charge-transfer resistances and improves the electrochemical performance and surface stability of the LiFePO 4 material in aqueous electrolyte solutions.

Theoretical study on the sound absorption of electrolytic solutions. I. Theoretical formulation.

PubMed

Yamaguchi, T; Matsuoka, T; Koda, S

2007-04-14

A theory is formulated that describes the sound absorption of electrolytic solutions due to the relative motion of ions, including the formation of ion pairs. The theory is based on the Kubo-Green formula for the bulk viscosity. The time correlation function of the pressure is projected onto the bilinear product of the density modes of ions. The time development of the product of density modes is described by the diffusive limit of the generalized Langevin equation, and approximate expressions for the three- and four-body correlation functions required are given with the hypernetted-chain integral equation theory. Calculations on the aqueous solutions of model electrolytes are performed. It is demonstrated that the theory describes both the activated barrier crossing between contact and solvent-separated ion pairs and the Coulombic correlation between ions.

Theoretical study on the sound absorption of electrolytic solutions. I. Theoretical formulation

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Matsuoka, T.; Koda, S.

2007-04-01

A theory is formulated that describes the sound absorption of electrolytic solutions due to the relative motion of ions, including the formation of ion pairs. The theory is based on the Kubo-Green formula for the bulk viscosity. The time correlation function of the pressure is projected onto the bilinear product of the density modes of ions. The time development of the product of density modes is described by the diffusive limit of the generalized Langevin equation, and approximate expressions for the three- and four-body correlation functions required are given with the hypernetted-chain integral equation theory. Calculations on the aqueous solutions of model electrolytes are performed. It is demonstrated that the theory describes both the activated barrier crossing between contact and solvent-separated ion pairs and the Coulombic correlation between ions.

Characterization of a membrane-based, electrochemically driven pumping system using aqueous electrolyte solutions.

PubMed

Norman, Mya A; Evans, Christine E; Fuoco, Anthony R; Noble, Richard D; Koval, Carl A

2005-10-01

Electrokinetic flow provides a mechanism for a variety of fluid pumping schemes. The design and characterization of an electrochemically driven pump that utilizes porous carbon electrodes, iodide/triiodide redox electrolytes, and Nafion membranes is described. Fluid pumping by the cell is reversible and controlled by the cell current. Chronopotentiometry experiments indicate that the total available fluid that can be pumped in a single electrolysis without gas evolution is determined solely by the initial concentration of electrolyte and the applied current. The magnitude of the fluid flow at a given current is determined by the nature of the cation in the electrolyte and by the water absorption properties of the Nafion membrane. For 1 M aqueous electrolytes, pumping rates ranging from 1 to 14 microL/min were obtained for current densities of 10-30 mA/cm2 of membrane area. Molar volume changes for the I3-/I- redox couple and for the alkali cation migration contribute little to the observed volumetric flow rates; the magnitude of the flow is dominated by the migration-induced flow of water.

Nanowire Na0.35MnO2 from a hydrothermal method as a cathode material for aqueous asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, B. H.; Liu, Y.; Chang, Z.; Yang, Y. Q.; Wen, Z. B.; Wu, Y. P.; Holze, R.

2014-05-01

Nanowire Na0.35MnO2 was prepared by a simple and low energy consumption hydrothermal method; its electrochemical performance as a cathode material for aqueous asymmetric supercapacitors in Na2SO4 solution was investigated. Due to the nanowire structure its capacitance (157 F g-1) is much higher than that of the rod-like Na0.95MnO2 (92 F g-1) from solid phase reaction although its sodium content is lower. When it is assembled into an asymmetric aqueous supercapacitor using activated carbon as the counter electrode and aqueous 0.5 mol L-1 Na2SO4 electrolyte solution, the nanowire Na0.35MnO2 shows an energy density of 42.6 Wh kg-1 at a power density of 129.8 W kg-1 based on the total weight of the two electrode material, higher than those for the rod-like Na0.95MnO2, with an energy density of 27.3 Wh kg-1 at a power density of 74.8 W kg-1, and that of LiMn2O4. The new material presents excellent cycling behavior even when dissolved oxygen is not removed from the electrolyte solution. The results hold great promise for practical applications of this cathode material since sodium is much cheaper than lithium and its natural resources are rich.

Addressing Student Misconceptions Concerning Electron Flow in Aqueous Solutions with Instruction Including Computer Animations and Conceptual Change Strategies.

ERIC Educational Resources Information Center

Sanger, Michael J.; Greenbowe, Thomas J.

2000-01-01

Investigates the effects of both computer animations of microscopic chemical processes occurring in a galvanic cell and conceptual-change instruction based on chemical demonstrations on students' conceptions of current flow in electrolyte solutions. Finds that conceptual change instruction was effective at dispelling student misconceptions but…

Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

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

Murugesan, Vijayakumar; Han, Kee Sung; Hu, Jianzhi

2017-03-19

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directlymore » involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.« less

Specific Anion Effects on Na+ Adsorption at the Aqueous Solution-Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments.

PubMed

Olivieri, Giorgia; Parry, Krista M; D'Auria, Raffaella; Tobias, Douglas J; Brown, Matthew A

2018-01-18

Specific ion effects of the large halide anions have been shown to moderate anion adsorption to the air-water interface (AWI), but little quantitative attention has been paid to the behavior of alkali cations. Here we investigate the concentration and local distribution of sodium (Na + ) at the AWI in dilute (<1 M) aqueous solutions of NaCl, NaBr, and NaI using a combination of molecular dynamics (MD) and SESSA simulations, and liquid jet ambient pressure photoelectron spectroscopy measurements. We use SESSA to simulate Na 2p photoelectron intensities on the basis of the atom density profiles obtained from MD simulations, and we compare the simulation results with photoelectron spectroscopy experiments to evaluate the performance of a nonpolarizable force field model versus that of an induced dipole polarizable one. Our results show that the nonpolarizable force model developed by Horinek and co-workers (Chem. Phys. Lett. 2009, 479, 173-183) accurately predicts the local concentration and distribution of Na + near the AWI for all three electrolytes, whereas the polarizable model does not. To our knowledge, this is the first interface-specific spectroscopic validation of a MD force field. The molecular origins of the unique Na + distributions for the three electrolytes are analyzed on the basis of electrostatic arguments, and shown to arise from an indirect anion effect wherein the identity of the anion affects the strength of the attractive Na + -H 2 O electrostatic interaction. Finally, we use the photoelectron spectroscopy results to constrain the range of inelastic mean free paths (IMFPs) for the three electrolyte solutions used in the SESSA simulations that are able to reproduce the experimental intensities. Our results suggest that earlier estimates of IMFPs for aqueous solutions are likely too high.

Electrochemical Studies of Sulfur Oxychlorides.

DTIC Science & Technology

1988-03-28

It had been proposed to study sulfuroxyhalides (1) as solutes in a non-aqueous solvent, (2) undiluted, employing lithium tetrachloroaluminate and (3...electrodes in N,N-dimethylforeamide (DNF) with tetra-butylammonium hexafluorophosphate (TBAPF6 ) as supporting electrolyte. Cyclic voltammetry showed

Anomalous cation diffusion in salt-doped confined bilayer ice.

PubMed

Qiu, Hu; Xue, Minmin; Shen, Chun; Guo, Wanlin

2018-05-17

The diffusive dynamics of aqueous electrolyte solutions in nanoconfined spaces has attracted considerable attention due to their potential applications in desalination, biosensors and supercapacitors. Here we show by molecular dynamics simulations that lithium and sodium ions diffuse at a rate at least an order of magnitude higher than that of water molecules when the ions are trapped in an ice bilayer confined between two parallel plates. This novel picture is in sharp contrast to the prevailing view that the diffusion rate of ions is comparable to or even lower than that of water in both bulk and confined solutions. The predicted high ion mobility stems from frequent lateral hopping of ions along the coordination sites inside the hydrogen-bonding network connecting the two water layers of the ice bilayer. This anomalous diffusion should provide new insights into the physics of confined aqueous electrolytes.

Convenient UV-spectrophotometric determination of citrates in aqueous solutions with applications in the pharmaceutical analysis of oral electrolyte formulations.

PubMed

Krukowski, Sylwester; Karasiewicz, Mateusz; Kolodziejski, Waclaw

2017-07-01

Herein, we present a convenient method for quantitative spectrophotometric determination of citrate ions in aqueous solutions in the middle-UV range. It involves measuring the absorbance of citric acid at 209 nm under suppressed dissociation at pH < 1.0 in the presence of hydrochloric acid. Validation of the method was performed according to the guidelines of the International Conference on Harmonization. A very good linear dependence of the absorbance on concentration (r 2  = 0.9999) was obtained in a citrate concentration range of 0.5-5.0 mmol/L. This method is characterized by excellent precision and accuracy; the coefficient of variation in each case is below the maximal permissible value (%RSD < 2). The proposed analytical procedure has been successfully applied to the determination of citrates in oral electrolyte formulations. Copyright © 2017. Published by Elsevier B.V.

Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James; Sun, Xuehui

2002-01-01

Novel fluorinated boronate-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boronate-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boronate-based anion receptors include different fluorinated alkyl and aryl groups.

High-performance carbon-coated ZnMn2O4 nanocrystallite supercapacitors with tailored microstructures enabled by a novel solution combustion method

NASA Astrophysics Data System (ADS)

Abdollahifar, Mozaffar; Huang, Sheng-Siang; Lin, Yu-Hsiang; Lin, Yan-Cheng; Shih, Bing-Yi; Sheu, Hwo-Shuenn; Liao, Yen-Fa; Wu, Nae-Lih

2018-02-01

Although ZnMn2O4 is widely studied as Li-ion battery anodes, it remains a challenge to tailor suitable microstructures of the oxide for supercapacitor applications. Carbon-coated ZnMn2O4 (C@ZMO) nanocrystallites showing high-performance pseudocapacitor behaviours in neutral aqueous electrolyte are for the first time successfully synthesised via a novel solution combustion process using polyethylene glycol as a multifunctional microstructure-directing agent. Controlling the molecular weight and amount of the polymer in the combustion solution enables the formation of highly-crystalline C@ZMO having substantially higher, by more than 5 folds, specific surface areas with mesoporous structures and conformal carbon coating via the one-pot synthesis process. The resulting C@ZMO supercapacitor electrodes in Na2SO4(aq) electrolyte exhibit ideal capacitive behaviours with specific capacitances up to 150 F g-1 and cycle stability showing no capacitance fade after 10,000 cycles at 60% of full capacity and >99% Coulombic efficiency. This study not only illustrates a new powerful synthesis route capable of producing conductive mesoporous crystalline oxide-based nanomaterials for energy storage applications but also reveals a new class of high-performance pseudocapacitive materials for neutral aqueous electrolytes.

Aqueous, Room Temperature Deposition of Silicon, Molybdenum and Germanium onto Aluminum Substrates

NASA Astrophysics Data System (ADS)

Krishnamurthy, Aarti Krishna

Electrochemical deposition of active materials such as Si, Mo and Ge is notoriously difficult, so they are typically deposited using expensive vacuum methods such as chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), and magnetron sputtering. However, for most materials, electrochemical deposition has significant advantages of cost, scalability, and manufacturability. There are two main challenges in depositing these materials from aqueous electrolytes at room temperature, namely their highly cathodic standard reduction potential and the formation of native oxides. This has led researchers to use non-aqueous electrolytes such as organic solvents, room temperature ionic liquids (RTILs), and high temperature molten salts. However, these have drawbacks over aqueous electrolytes such as high cost, low conductivity, flammability, and corrosive behavior. During my PhS studies, these two challenges were overcome by using the galvanic method of deposition and by including HF in the electrolyte. Si thin films are employed in a variety of technologies, including microelectronic and photovoltaic devices, Li ion battery anodes, and corrosion-resistant coatings. A galvanic and a combined galvanic/electroless method of Si deposition were developed using aqueous electrolytes at room temperature to obtain nanoporous and compact films, respectively. These films were characterized to understand the surface morphology, thickness, crystallinity, growth rate, composition and nucleation behavior. Approximately 7-10 µm thick compact Si films were achieved with a deposition time of around 28 hours. The galvanic method of deposition was also extended to deposit compact Mo films. Mo thin films have a number of technological applications, including back contacts for CIGS/CZTS photovoltaic devices and corrosion-resistant coatings. Mo thin films were also thoroughly characterized and approximately 4.5 µm thick films were obtained after 3 hours. Similar to Si depostion, a galvanic method of deposition and the galvanic/electroless method of deposition was tested for the deposition of Ge. However no Ge deposit could be consistently obtained, probably due to oxyanion formation in aqueous hexaflurogermante solution.

Band edge engineering of oxide photoanodes for photoelectrochemical water splitting: Integration of subsurface dipoles with atomic-scale control

DOE PAGES

Hikita, Yasuyuki; Nishio, Kazunori; Seitz, Linsey C.; ...

2016-01-22

One of the crucial parameters dictating the efficiency of photoelectrochemical water-splitting is the semiconductor band edge alignment with respect to hydrogen and oxygen redox potentials. Despite the importance of metal oxides in their use as photoelectrodes, studies to control the band edge alignment in aqueous solution have been limited predominantly to compound semiconductors with modulation ranges limited to a few hundred mV. The ability to modulate the flat band potential of oxide photoanodes by as much as 1.3 V, using the insertion of subsurface electrostatic dipoles near a Nb-doped SrTiO 3/aqueous electrolyte interface is reported. Lastly, the tunable range achievedmore » far exceeds previous reports in any semiconductor/aqueous electrolyte system and suggests a general design strategy for highly efficient oxide photoelectrodes.« less

Aqueous NaCl and CsCl Solutions Confined in Crystalline Slit-Shaped Silica Nanopores of Varying Degree of Protonation

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

Ho, Tuan A.; Argyris, Dimitrios; Cole, David R.

2011-12-13

All-atom molecular dynamics simulations were conducted to study the dynamics of aqueous electrolyte solutions confined in slit-shaped silica nanopores of various degrees of protonation. Five degrees of protonation were prepared by randomly removing surface hydrogen atoms from fully protonated crystalline silica surfaces. Aqueous electrolyte solutions containing NaCl or CsCl salt were simulated at ambient conditions. In all cases, the ionic concentration was 1 M. The results were quantified in terms of atomic density distributions within the pores, and the self-diffusion coefficient along the direction parallel to the pore surface. We found evidence for ion-specific properties that depend on ion-surface, water-ion,more » and only in some cases ion-ion correlations. The degree of protonation strongly affects the structure, distribution, and the dynamic behavior of confined water and electrolytes. Cl -ions adsorb on the surface at large degrees of protonation, and their behavior does not depend significantly on the cation type (either Na + or Cs + ions are present in the systems considered). The cations show significant ion-specific behavior. Na + ions occupy different positions within the pore as the degree of protonation changes, while Cs + ions mainly remain near the pore center at all conditions considered. For a given degree of protonation, the planar self-diffusion coefficient of Cs + is always greater than that of Na + ions. The results are useful for better understanding transport under confinement, including brine behavior in the subsurface, with important applications such as environmental remediation.« less

METHOD AND APPARATUS FOR DETERMINING AMALGAM DECOMPOSITION RATE

DOEpatents

Johnson, R.W.; Wright, C.C.

1962-04-24

A method and apparatus for measuring the rate at which an amalgam decomposes in contact with aqueous solutions are described. The amalgam and an aqueous hydroxide solution are disposed in an electrolytic cell. The amalgam is used as the cathode of the cell, and an electrode and anode are disposed in the aqueous solution. A variable source of plating potential is connected across the cell. The difference in voltage between the amalgam cathode and a calibrated source of reference potential is used to control the variable source to null the difference in voltage and at the same time to maintain the concentration of the amalgam at some predetermined constant value. The value of the current required to maintain this concentration constant is indicative of the decomposition rate of the amalgam. (AEC)

The impact of pH on side reactions for aqueous redox flow batteries based on nitroxyl radical compounds

NASA Astrophysics Data System (ADS)

Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S.

2016-07-01

Electrochemical and UV-VIS measurements demonstrate that the pH value of a 4-hydroxy-2,2,6,6-tetramethyl-1-pipperidinyloxyl (TEMPOL) electrolyte significantly impacts its redox reversibility. The diffusion coefficient and kinetic rate constant of TEMPOL in neutral aqueous solution are determined and shown to be comparable to those of vanadium ions used for industrially utilized redox flow batteries (RFBs). RFBs that incorporate a TEMPOL catholyte and Zn-based anolyte have an average voltage of 1.46 V and an energy efficiency of 80.4% during the initial cycle, when subject to a constant current of 10 mA cm-2. We demonstrate several factors that significantly influence the concentration and capacity retention of TEMPOL upon cycling; namely, pH and atmospheric gases dissolved in electrolyte. We expand upon the known reactions of TEMPOL in aqueous electrolyte and propose several concepts to improve its electrochemical performance in a RFB. Controlling these factors will be the key to enable the successful implementation of this relatively inexpensive and environmentally friendly battery.

Capacitive behaviour of MnF2 and CoF2 submicro/nanoparticles synthesized via a mild ionic liquid-assisted route

NASA Astrophysics Data System (ADS)

Ma, Ruguang; Zhou, Yao; Yao, Lin; Liu, Guanghui; Zhou, Zhenzhen; Lee, Jong-Min; Wang, Jiacheng; Liu, Qian

2016-01-01

Submicro-/nano-sized MnF2 rods and hierarchical CoF2 cuboids are respectively synthesized via a facile precipitation method assisted by ionic liquid under a mild condition. The as-prepared MF2 (M = Mn, Co) submicro/nanoparticles exhibit impressive specific capacitance in 1.0 M KOH aqueous solution, especially at relatively high current densities, e.g. 91.2, 68.7 and 56.4 F g-1 for MnF2, and 81.7, 70.6 and 63.0 F g-1 for CoF2 at 5, 8 and 10 A g-1, respectively. The mechanism of striking capacitance of MF2 is clarified on the basis of analysing the cycled electrodes by different characterization techniques. Such remarkable capacitance is ascribed to the redox reactions between MF2 and MOOH in aqueous alkaline electrolytes, which can not be obtained in aqueous neutral electrolytes. This study for the first time provides direct evidences on the pseudocapacitance mechanism of MF2 in alkaline electrolytes and paves the way of application of transition metal fluorides as electrodes in supercapacitors.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

DOEpatents

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Solubility of NaCl in aqueous electrolyte solutions from 10 to 100°C

USGS Publications Warehouse

Clynne, M.A.; Potter, R.W.; Haas, J.L.

1981-01-01

The solubilities of NaCl in aqueous KCl, MgCl2, CaCl2, and mixed CaCl2-KCl solutions have been determined from 10 to 100??C. The data were fit to an equation, and the equation was used to calculate values of the change in solubility of NaCl, ???[NaCl]/???T. These values are required for calculations of the rate of migration of fluids in a thermal gradient in rock salt. The data obtained here indicate that the values of ???[NaCl]/???T are 36-73% greater for solutions containing divalent ions than for the NaCl-H2O system.

[Computer modeling the hydrostatic pressure characteristics of the membrane potential for polymeric membrane, separated non-homogeneous electrolyte solutions].

PubMed

Slezak, Izabella H; Jasik-Slezak, Jolanta; Rogal, Mirosława; Slezak, Andrzej

2006-01-01

On the basis of model equation depending the membrane potential deltapsis, on mechanical pressure difference (deltaP), concentration polarization coefficient (zetas), concentration Rayleigh number (RC) and ratio concentration of solutions separated by membrane (Ch/Cl), the characteristics deltapsis = f(deltaP)zetas,RC,Ch/Cl for steady values of zetas, RC and Ch/Cl in single-membrane system were calculated. In this system neutral and isotropic polymeric membrane oriented in horizontal plane, the non-homogeneous binary electrolytic solutions of various concentrations were separated. Nonhomogeneity of solutions is results from creations of the concentration boundary layers on both sides of the membrane. Calculations were made for the case where on a one side of the membrane aqueous solution of NaCl at steady concentration 10(-3) mol x l(-1) (Cl) was placed and on the other aqueous solutions of NaCl at concentrations from 10(-3) mol x l(-1) to 2 x 10(-2) mol x l(-1) (Ch). Their densities were greater than NaCl solution's at 10(-3) mol x l(-1). It was shown that membrane potential depends on hydrodynamic state of a complex concentration boundary layer-membrane-concentration boundary layer, what is controlled by deltaP, Ch/Cl, RC and zetas.

Glass cylindrical filter for electrolysis cell

NASA Astrophysics Data System (ADS)

Abe, Shinichi; Akiyama, Fuminori

1992-09-01

Some electrolysis requires separation of electrolytic solution by a filter between two electrodes in order to prevent products from reacting secondarily at another electrode. These filters are usually made of a glass filter or ion exchanger membrane, and they are fixed at the electrolysis cell or cover one electrode. This report presents a detachable glass cylindrical filter for electrolytic reaction. The glass cylindrical filter was made from glass filter powder placed in a mold and heated at 800 C for 18 minutes. Using this filter, electrolytic reduction of carbon dioxide was performed in 0 C hot water with benzoin. This reaction produces aqueous oil from carbon dioxide and water. The products were compared with and without the filter and, although the yield did not differ between the two reaction systems, products without the filter contained highly polymerized oil compared to those with the filter. This suggests that the aqueous oil was produced at the cathode and polymerized at the anode.

Electrochemistry serving people and nature: high-energy ecocapacitors based on redox-active electrolytes.

PubMed

Frackowiak, Elzbieta; Fic, Krzysztof; Meller, Mikolaj; Lota, Grzegorz

2012-07-01

Positive Poles: A new type of electrochemical capacitor with two different aqueous solutions, separated by a Nafion membrane is described. High capacitance values as well as excellent energy/power characteristics are reported and discussed. The neutral character of the applied electrolytes makes this capacitor an environmentally friendly, easy to assemble, and cost-effective device for energy storage. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous Protein-Protein Interactions in Multivalent Salt Solution.

PubMed

Pasquier, Coralie; Vazdar, Mario; Forsman, Jan; Jungwirth, Pavel; Lund, Mikael

2017-04-13

The stability of aqueous protein solutions is strongly affected by multivalent ions, which induce ion-ion correlations beyond the scope of classical mean-field theory. Using all-atom molecular dynamics (MD) and coarse grained Monte Carlo (MC) simulations, we investigate the interaction between a pair of protein molecules in 3:1 electrolyte solution. In agreement with available experimental findings of "reentrant protein condensation", we observe an anomalous trend in the protein-protein potential of mean force with increasing electrolyte concentration in the order: (i) double-layer repulsion, (ii) ion-ion correlation attraction, (iii) overcharge repulsion, and in excess of 1:1 salt, (iv) non Coulombic attraction. To efficiently sample configurational space we explore hybrid continuum solvent models, applicable to many-protein systems, where weakly coupled ions are treated implicitly, while strongly coupled ones are treated explicitly. Good agreement is found with the primitive model of electrolytes, as well as with atomic models of protein and solvent.

Rate of Bubble Coalescence following Quasi-Static Approach: Screening and Neutralization of the Electric Double Layer

PubMed Central

Katsir, Yael; Marmur, Abraham

2014-01-01

Air-bubble coalescence in aqueous electrolytic solutions, following quasi-static approach, was studied in order to understand its slow rate in purified water and high rate in electrolytic solutions. The former is found to be due to surface charges, originating from the speciation of dissolved CO2, which sustain the electric double layer repulsion. Rapid coalescence in electrolytic solutions is shown to occur via two different mechanisms: (1) neutralization of the carbonaceous, charged species by acids; or (2) screening of the repulsive charge effects by salts and bases. The results do not indicate any ion specificity. They can be explained within the DLVO theory for the van der Waals and electric double layer interactions between particles, in contrast to observations of coalescence following dynamic approach. The present conclusions should serve as a reference point to understanding the dynamic behavior. PMID:24589528

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

NASA Astrophysics Data System (ADS)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li-air battery. Towards this end, using either tetrabutylammonium hexafluorophosphate (TBAPF6) or lithium hexafluorophosphate (LiPF6) electrolyte solutions in four different solvents, namely, dimethyl sulfoxide (DMSO), acetonitrile (MeCN), dimethoxyethane (DME), and tetraethylene glycol dimethyl ether (TEGDME), possessing a range of properties, we have determined that the solvent and the supporting electrolyte cations in the solution act in concert to influence the nature of reduction products and their rechargeability. In solutions containing TBA +, O2 reduction is a highly reversible one-electron process involving the O2/O2- couple in all of the electrolytes examined with little effect on the nature of the solvent. On the other hand, in Li+-containing electrolytes relevant to the Li-air battery, O2 reduction proceeds in a stepwise fashion to form O2-, O22- and O2- as products. These reactions in presence of Li+ are irreversible or quasi-reversible electrochemical processes and the solvents have significant influence on the kinetics, and reversibility or lack thereof, of the different reduction products. Reversible reduction of O2 to long-lived superoxide in a Li+-conducting electrolyte in DMSO has been shown for the first time here. Chapter 5 is the culmination of the thesis where the practical application of the work is demonstrated. We designed electrolytes that facilitate Li-Air rechargeability, by applying the knowledge gained from chapters 2-4. A rechargeable Li-air cell utilizing an electrolyte composed of a solution of LiPF6 in tetraethylene glycol dimethyl ether, CH3O(CH2CH 2O)4CH3 was designed, built and its performance studied. It was shown that the cell yields high capacity and can be recharged in spite the absence of catalyst in the carbon cathode. The application of X-ray diffraction to identify these products formed in a porous carbon electrode is shown here for the first time. The rechargeability of the cell was investigated by repeated charge/discharge cycling of the cell, and the factors limiting the cycle life of the cell were studied using AC impedance spectra of the cells as a function of cycle number. In conclusion, the work carried out in this research has shown that the O2 electrochemistry in organic electrolytes is substantially different from that in aqueous electrolytes. Our work has uncovered the key roles the ion conducting salts and the organic solvents play in determining the nature of the reduction products and their reversibility. The results presented here for the first time provide a rational approach to the design and selection of organic electrolyte solutions for use in the rechargeable Li-air battery. (Abstract shortened by UMI.)

Ceramic electrolyte coating and methods

DOEpatents

Seabaugh, Matthew M [Columbus, OH; Swartz, Scott L [Columbus, OH; Dawson, William J [Dublin, OH; McCormick, Buddy E [Dublin, OH

2007-08-28

Aqueous coating slurries useful in depositing a dense coating of a ceramic electrolyte material (e.g., yttrium-stabilized zirconia) onto a porous substrate of a ceramic electrode material (e.g., lanthanum strontium manganite or nickel/zirconia) and processes for preparing an aqueous suspension of a ceramic electrolyte material and an aqueous spray coating slurry including a ceramic electrolyte material. The invention also includes processes for depositing an aqueous spray coating slurry including a ceramic electrolyte material onto pre-sintered, partially sintered, and unsintered ceramic substrates and products made by this process.

Thiocyanates as attractive redox-active electrolytes for high-energy and environmentally-friendly electrochemical capacitors.

PubMed

Gorska, Barbara; Bujewska, Paulina; Fic, Krzysztof

2017-03-15

This manuscript reports on the novel insight into the development of high voltage carbon/carbon electrochemical capacitors operating in aqueous solutions of alkali metals and ammonium thiocyanates (KSCN, NaSCN, LiSCN, and NH 4 SCN). The effect of salt concentration, electrode porosity and current collectors on the capacitance value, system stability, and power performance has been investigated. Therefore, thiocyanate-based electrolytes were recognized as cheap and highly conductive electrolytic solutions (up to 401 mS cm -1 for NH 4 SCN at RT) allowing a cell voltage of 1.6 V in a symmetric carbon/carbon system to be achieved. At the same time, they display an attractive redox activity, enhancing the energy of the device with a good performance during cycling.

Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields.

PubMed

Moučka, Filip; Nezbeda, Ivo; Smith, William R

2015-04-14

We describe a computationally efficient molecular simulation methodology for calculating the concentration dependence of the chemical potentials of both solute and solvent in aqueous electrolyte solutions, based on simulations of the salt chemical potential alone. We use our approach to study the predictions for aqueous NaCl solutions at ambient conditions of these properties by the recently developed polarizable force fields (FFs) AH/BK3 of Kiss and Baranyai (J. Chem. Phys. 2013, 138, 204507) and AH/SWM4-DP of Lamoureux and Roux (J. Phys. Chem. B 2006, 110, 3308 - 3322) and by the nonpolarizable JC FF of Joung and Cheatham tailored to SPC/E water (J. Phys. Chem. B 2008, 112, 9020 - 9041). We also consider their predictions of the concentration dependence of the electrolyte activity coefficient, the crystalline solid chemical potential, the electrolyte solubility, and the solution specific volume. We first highlight the disagreement in the literature concerning calculations of solubility by means of molecular simulation in the case of the JC FF and provide strong evidence of the correctness of our methodology based on recent independently obtained results for this important test case. We then compare the predictions of the three FFs with each other and with experiment and draw conclusions concerning their relative merits, with particular emphasis on the salt chemical potential and activity coefficient vs concentration curves and their derivatives. The latter curves have only previously been available from Kirkwood-Buff integrals, which require approximate numerical integrations over system pair correlation functions at each concentration. Unlike the case of the other FFs, the AH/BK3 curves are nearly parallel to the corresponding experimental curves at moderate and higher concentrations. This leads to an excellent prediction of the water chemical potential via the Gibbs-Duhem equation and enables the activity coefficient curve to be brought into excellent agreement with experiment by incorporating an appropriate value of the standard state chemical potential in the Henry Law convention.

The self-association of acebutolol: Conductometry and light scattering

NASA Astrophysics Data System (ADS)

Ruso, Juan M.; López-Fontán, José L.; Prieto, Gerardo; Sarmiento, Félix

2003-04-01

The association characteristics of an amphiphilic beta-blocker drug, acebutolol hydrochloride, in aqueous solution containing high concentrations of electrolyte and at different temperatures have been examined by static and dynamic light scattering and electrical conductivity. Time averaged light scattering measurements on aqueous solutions of acebutolol at 298.15 K in the presence of added electrolyte (0.4-1.0 mol kg-1 NaCl) have shown discontinuities which reflect the appearance of aggregates. The critical micelle concentration, aggregation numbers, effective micelle charges, and degree of micellar ionization were calculated. Dynamic light scattering has shown an increase in micellar size with increase in concentration of added electrolyte. Data have been interpreted using the DLVO theory to quantify the interaction between the drug aggregates and the colloidal stability. Critical micelle concentrations in water have been calculated from conductivity measurements over the temperature range 288.15-313.15 K. The variation in critical concentration with temperature passes through a minimum close to 294 K. Thermodynamic parameters of aggregate formation (ΔGm0,ΔHm0,ΔSm0) were obtained from a variation of the mass action model applicable to systems of low aggregation number.

Molecular simulation of aqueous electrolyte solubility. 2. Osmotic ensemble Monte Carlo methodology for free energy and solubility calculations and application to NaCl.

PubMed

Moučka, Filip; Lísal, Martin; Škvor, Jiří; Jirsák, Jan; Nezbeda, Ivo; Smith, William R

2011-06-23

We present a new and computationally efficient methodology using osmotic ensemble Monte Carlo (OEMC) simulation to calculate chemical potential-concentration curves and the solubility of aqueous electrolytes. The method avoids calculations for the solid phase, incorporating readily available data from thermochemical tables that are based on well-defined reference states. It performs simulations of the aqueous solution at a fixed number of water molecules, pressure, temperature, and specified overall electrolyte chemical potential. Insertion/deletion of ions to/from the system is implemented using fractional ions, which are coupled to the system via a coupling parameter λ that varies between 0 (no interaction between the fractional ions and the other particles in the system) and 1 (full interaction between the fractional ions and the other particles of the system). Transitions between λ-states are accepted with a probability following from the osmotic ensemble partition function. Biasing weights associated with the λ-states are used in order to efficiently realize transitions between them; these are determined by means of the Wang-Landau method. We also propose a novel scaling procedure for λ, which can be used for both nonpolarizable and polarizable models of aqueous electrolyte systems. The approach is readily extended to involve other solvents, multiple electrolytes, and species complexation reactions. The method is illustrated for NaCl, using SPC/E water and several force field models for NaCl from the literature, and the results are compared with experiment at ambient conditions. Good agreement is obtained for the chemical potential-concentration curve and the solubility prediction is reasonable. Future improvements to the predictions will require improved force field models.

Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li-O2 batteries

NASA Astrophysics Data System (ADS)

Aetukuri, Nagaphani B.; McCloskey, Bryan D.; García, Jeannette M.; Krupp, Leslie E.; Viswanathan, Venkatasubramanian; Luntz, Alan C.

2015-01-01

Given their high theoretical specific energy, lithium-oxygen batteries have received enormous attention as possible alternatives to current state-of-the-art rechargeable Li-ion batteries. However, the maximum discharge capacity in non-aqueous lithium-oxygen batteries is limited to a small fraction of its theoretical value due to the build-up of insulating lithium peroxide (Li2O2), the battery’s primary discharge product. The discharge capacity can be increased if Li2O2 forms as large toroidal particles rather than as a thin conformal layer. Here, we show that trace amounts of electrolyte additives, such as H2O, enhance the formation of Li2O2 toroids and result in significant improvements in capacity. Our experimental observations and a growth model show that the solvating properties of the additives prompt a solution-based mechanism that is responsible for the growth of Li2O2 toroids. We present a general formalism describing an additive’s tendency to trigger the solution process, providing a rational design route for electrolytes that afford larger lithium-oxygen battery capacities.

Method of making chalcogen catalysts for polymer electrolyte fuel cells

DOEpatents

Choi, Jong-Ho; Zelenay, Piotr; Wieckowski, Andrzej; Cao, Dianxue

2010-12-14

A method of making an electrode catalyst material using aqueous solutions. The electrode catalyst material includes a support comprising at least one transition metal and at least one chalcogen disposed on a surface of the transition metal. The method includes reducing a metal powder, mixing the metal powder with an aqueous solution containing at least one inorganic compound of the chalcogen to form a mixture, and providing a reducing agent to the mixture to form nanoparticles of the electrode catalyst. The electrode catalyst may be used in a membrane electrode assembly for a fuel cell.

Synthetic carbonaceous fuels and feedstocks

DOEpatents

Steinberg, Meyer

1980-01-01

This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends. The oxygen generated at the anode is preferably vented into the atmosphere, and the regenerated sodium hydroxide produced at the cathode is reused for scrubbing the CO.sub.2 from the atmosphere.

Mineralization of aniline in aqueous solution by electrochemical activation of persulfate.

PubMed

Chen, Wen-Shing; Huang, Chi-Pin

2015-04-01

Oxidative degradation of aniline in aqueous solution was carried out by coupling electrolysis with persulfate oxidation, in which a synergistic effect occurred. Experiments were performed under a batch-wise mode to evaluate the influence of various operation parameters on the electrolytic behavior, such as acidity of aqueous solution, temperature, electrode potential, persulfate anion concentration and nitrogen/oxygen gas dosage. The aniline pollutants could be almost entirely mineralized by means of electro-activated persulfate oxidation, wherein sulfate radicals were presumed to be principal oxidizing agents. Besides, electrogenerated hydrogen peroxide originated from cathodic reduction of oxygen, supplied chiefly by anodic oxidation of water, would contribute partially for decomposition of aniline. On the whole, the electro-activated persulfate process is a very promising method for treatment of aniline in wastewater. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PALLADIUM-FACILITATED ELECTROLYTIC DECHLORINATION OF 2-CHLOROBIPHENYL USING A GRANULAR-GRAPHITE ELECTRODE.

EPA Science Inventory

Palladium-assisted electrocatalytic dechlorination of 2-chlorobiphenyl (2-Cl BP) in aqueous solutions was conducted in a membrane-separated electrochemical reactor with granular-graphite packed electrodes. The dechlorination took place at a granular-graphite cathode while Pd was ...

Evolution of Osmolyte Systems.

ERIC Educational Resources Information Center

Banfalvi, Gaspar

1991-01-01

Osmotic aspects of aqueous solutions that are usually disregarded in biochemistry textbooks are presented. This article discusses the osmolarity of seawater, evolution of organisms over geological time, ionic adaptation of cells, ionic concentrations in bacteria, osmolytes and blood electrolytes in water-stressed organisms and land vertebrates,…

Effects of sulfate and nitrate anions on aluminum corrosion in slightly alkaline solution

NASA Astrophysics Data System (ADS)

Li, Shengyi; Church, Benjamin C.

2018-05-01

The corrosion mechanisms and kinetics of AA1085 in Li2SO4 and LiNO3 aqueous rechargeable lithium-ion battery electrolytes were investigated at pH 11 using chronoamperometry. The corrosion kinetics of AA1085 is controlled by the electrolyte concentration level and the anodic potentials. AA1085 is susceptible to crystallographic pitting corrosion in Li2SO4 electrolytes. The rates of pit nucleation and pit growth both decreased at higher Li2SO4 concentrations or at lower anodic potentials. AA1085 passivates against pitting corrosion in LiNO3 electrolytes due to the formation of a thick, uniform corrosion product layer. The growth rate of the passive film was slightly enhanced by increasing the electrolyte concentration and anodic potentials. X-ray photoelectron spectroscopy spectra showed the formation of a thin sulfate-incorporated passive film on the electrode, which comprises Al2(SO)418H2O, Al(OH)SO4 and Al(OH)3, before the occurrence of pitting growth in 2 M Li2SO4 electrolyte. The thick corrosion product layer formed in 5 M LiNO3 electrolyte was composed of Al(OH)3 and AlOOH. Raman spectroscopy on deionized water, LiOH solution, Li2SO4 and LiNO3 electrolytes depicted changes of solution structure with increasing electrolyte concentration. The influence of extrinsic and intrinsic factors on the corrosion kinetics of AA1085 in Li2SO4 and LiNO3 electrolytes at pH 11 are discussed in detail.

Ceramic electrolyte coating methods

DOEpatents

Seabaugh, Matthew M.; Swartz, Scott L.; Dawson, William J.; McCormick, Buddy E.

2004-10-12

Processes for preparing aqueous suspensions of a nanoscale ceramic electrolyte material such as yttrium-stabilized zirconia. The invention also includes a process for preparing an aqueous coating slurry of a nanoscale ceramic electrolyte material. The invention further includes a process for depositing an aqueous spray coating slurry including a ceramic electrolyte material on pre-sintered, partially sintered, and unsintered ceramic substrates and products made by this process.

Boron compounds as anion binding agents for nonaqueous battery electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xia-Oing; McBreen, James; Xiang, Caili

2000-02-08

Novel fluorinated boron-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boron-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boron-based anion receptors include borane and borate compounds bearing different fluorinated alkyl and aryl groups.

Effects of electrode distance and nature of electrolyte on the diameter of titanium dioxide nanotube

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

Abbasi, S., E-mail: sum.abbasi@gmail.com; Mohamed, N. M., E-mail: noranimuti-mohamed@petronas.com.my; Singh, B. S. M., E-mail: balbir@petronas.com.my

2015-07-22

The titanium nanotubes were synthesized using viscous electrolytes consisting of ethylene glycol and non-viscous electrolytes consisting of aqueous solution of hydrofluoric acid. Sodium fluoride and ammonium fluoride were utilized as the source of fluorine ions. The samples were then characterized by field emission scanning electron microscope (FE-SEM). Their morphologies were investigated under different anodic potentials and various electrolyte compositions. It was found out that nanotubes can be obtained in fluoride ions and morphology is dependent on various parameters like anodic potential, time, electrolyte composition and the effects by varying the distance between the electrodes on the morphology was also investigated.more » It was found that by altering the distance between the electrodes, change in the diameter and the porosity was observed.« less

Redox shuttles for overcharge protection of lithium batteries

DOEpatents

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

Alkaline electrochemical cells and method of making

NASA Technical Reports Server (NTRS)

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

1970-01-01

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

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

PubMed Central

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-01-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ∼3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries. PMID:28585527

Organic hydrogen peroxide-driven low charge potentials for high-performance lithium-oxygen batteries with carbon cathodes

NASA Astrophysics Data System (ADS)

Wu, Shichao; Qiao, Yu; Yang, Sixie; Ishida, Masayoshi; He, Ping; Zhou, Haoshen

2017-06-01

Reducing the high charge potential is a crucial concern in advancing the performance of lithium-oxygen batteries. Here, for water-containing lithium-oxygen batteries with lithium hydroxide products, we find that a hydrogen peroxide aqueous solution added in the electrolyte can effectively promote the decomposition of lithium hydroxide compounds at the ultralow charge potential on a catalyst-free Ketjen Black-based cathode. Furthermore, for non-aqueous lithium-oxygen batteries with lithium peroxide products, we introduce a urea hydrogen peroxide, chelating hydrogen peroxide without any water in the organic, as an electrolyte additive in lithium-oxygen batteries with a lithium metal anode and succeed in the realization of the low charge potential of ~3.26 V, which is among the best levels reported. In addition, the undesired water generally accompanying hydrogen peroxide solutions is circumvented to protect the lithium metal anode and ensure good battery cycling stability. Our results should provide illuminating insights into approaches to enhancing lithium-oxygen batteries.

Dual Electrolytic Plasma Processing for Steel Surface Cleaning and Passivation

NASA Astrophysics Data System (ADS)

Yang, L.; Zhang, P.; Shi, J.; Liang, J.; Tian, W. B.; Zhang, Y. M.; Sun, Z. M.

2017-10-01

To remove the rust on rebars and passivate the fresh surfaces, electrodes reversing electrolytic plasma processing (EPP) was proposed and conducted in a 10 wt.% Na2CO3 aqueous solution. The morphology and the composition of the surface were investigated by SEM and XPS. Experimental results show that the rust on the surface was removed effectively by cathode EPP, and a passive film containing Cr2O3 was achieved by the succeeding anode EPP treatment, by a simple operation of reversing the bias. The corrosion resistance was evaluated in a 3.5 wt.% NaCl aqueous solution using an electrochemical workstation. In comparison, the corrosion resistance was improved by the succeeding anode EPP treatment, which is evidenced by a positive shift of the open-circuit potential, an increase in the electrochemical impedance representing the inner layer by 76.8% and the decrease in the corrosion current density by 49.6%. This is an effective and environment-friendly technique to clean and passivate rebars and similar steel materials.

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual-Electrolyte Sodium-Ion Battery.

PubMed

Senthilkumar, Sirugaloor Thangavel; Bae, Hyuntae; Han, Jinhyup; Kim, Youngsik

2018-05-04

A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na + ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na 4 Fe(CN) 6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Na x -NiBP) as the Na + ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na 2 SO 4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Computer modeling the dependences of the membrane potential for polymeric membrane separated non-homogeneous electrolyte solutions on concentration Rayleigh number].

PubMed

Slezak, Izabella H; Jasik-Slezak, Jolanta; Bilewicz-Wyrozumska, Teresa; Slezak, Andrzej

2006-01-01

On the basis of model equation describing the membrane potential delta psi(s) on concentration Rayleigh number (R(C)), mechanical pressure difference (deltaP), concentration polarization coefficient (zeta s) and ratio concentration of solutions separated by membrane (Ch/Cl), the characteristics delta psi(s) = f(Rc)(delta P, zeta s, Ch/Cl) for steady values of zeta s, R(C) and Ch/Cl in single-membrane system were calculated. In this system neutral and isotropic polymeric membrane oriented in horizontal plane, the non-homogeneous binary electrolytic solutions of various concentrations were separated. Nonhomogeneity of solutions is results from creations of the concentration boundary layers on both sides of the membrane. Calculations were made for the case where on a one side of the membrane aqueous solution of NaCl at steady concentration 10(-3) mol x l(-1) (Cl) was placed and on the other aqueous solutions of NaCl at concentrations from 10(-3) mol x l(-1) to 2 x 10(-2) mol x l(-1) (Ch). Their densities were greater than NaCl solution's at 10(-3) mol x l(-1). It was shown that membrane potential depends on hydrodynamic state of a complex concentration boundary layer-membrane-concentration boundary layer, what is controlled by deltaP, Ch/Cl, Rc and Zeta(s).

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

DOE PAGES

Li, Bin; Nie, Zimin; Vijayakumar, M.; ...

2015-02-24

Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L -1) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI 2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L -1 at the solubility limit of ZnI 2 in water (~7 M).more » We demonstrate charge and discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI 2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI 2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.« less

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

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

Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David

Here, we report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performancemore » in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.« less

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes.

PubMed

Giovannitti, Alexander; Maria, Iuliana P; Hanifi, David; Donahue, Mary J; Bryant, Daniel; Barth, Katrina J; Makdah, Beatrice E; Savva, Achilleas; Moia, Davide; Zetek, Matyáš; Barnes, Piers R F; Reid, Obadiah G; Inal, Sahika; Rumbles, Garry; Malliaras, George G; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

2018-05-08

We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

DOE PAGES

Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; ...

2018-04-24

Here, we report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performancemore » in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.« less

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of Nanoparticles and Colloids in Aquatic Systems 1. Small Angle Neutron Scattering Investigations of Suwannee River Fulvic Acid Aggregates in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Diallo, Mamadou S.; Glinka, Charles J.; Goddard, William A.; Johnson, James H.

2005-10-01

Fulvic acids (FA) and humic acids (HA) constitute 30-50% of dissolved organic matter in natural aquatic systems. In aqueous solutions, a commonly accepted view is that FA and HA exist as soluble macroligands at low concentration and as supramolecular aggregates at higher concentration. The size, shape and structure of these aggregates are still the subject of ongoing debate in the environmental chemistry literature. In this article, we use small angle neutron scattering (SANS) to assess the effects of solute concentration, solution pH and background electrolyte (NaCl) concentration on the structures of Suwannee River FA (SRFA) aggregates in D2O. The qualitative features of the SANS curves and data analysis are not consistent with the view point that SRFA forms micelle-like aggregates as its concentration in aqueous solution increases. We find that SRFA forms fractal aggregates in D20 with size greater than 242 nm. The SRFA aggregates undergo a significant degree of restructuring in compactness as solution pH, solute concentration and NaCl concentration increase.

Measurement of Setschenow constants for six hydrophobic compounds in simulated brines and use in predictive modeling for oil and gas systems.

PubMed

Burant, Aniela; Lowry, Gregory V; Karamalidis, Athanasios K

2016-02-01

Treatment and reuse of brines, produced from energy extraction activities, requires aqueous solubility data for organic compounds in saline solutions. The presence of salts decreases the aqueous solubility of organic compounds (i.e. salting-out effect) and can be modeled using the Setschenow Equation, the validity of which has not been assessed in high salt concentrations. In this study, we used solid-phase microextraction to determine Setschenow constants for selected organic compounds in aqueous solutions up to 2-5 M NaCl, 1.5-2 M CaCl2, and in Na-Ca binary electrolyte solutions to assess additivity of the constants. These compounds exhibited log-linear behavior up to these high NaCl concentrations. Log-linear decreases in solubility with increasing salt concentration were observed up to 1.5-2 M CaCl2 for all compounds, and added to a sparse database of CaCl2 Setschenow constants. Setschenow constants were additive in binary electrolyte mixtures. New models to predict CaCl2 and KCl Setschenow constants from NaCl Setschenow constants were developed, which successfully predicted the solubility of the compounds measured in this study. Overall, data show that the Setschenow Equation is valid for a wide range of salinity conditions typically found in energy-related technologies. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel aqueous dual-channel aluminum-hydrogen peroxide battery

NASA Astrophysics Data System (ADS)

Marsh, Catherine; Licht, Stuart

1994-06-01

A dual-channel aluminum hydrogen peroxide battery is introduced with an open-circuit voltage of 1.9 volts, polarization losses of 0.9 mV cm(exp 2) mA(exp -1), and power densities of 1 W/cm(exp 2). Catholyte and anolyte cell compartments are separated by an Ir/Pd modified porous nickel cathode. Separation of catholyte and anolyte chambers prevents hydrogen peroxide poisoning of the aluminum anode. The battery is expressed by aluminum oxidation and aqueous solution phase hydrogen peroxide reduction for an overall battery discharge consisting of 2Al + 3H2O2 + 2OH(-) yields 2AlO2(-) + 4H2O E = 2.3 V. The search for electrical propulsion sources which fit the requirements for electrically powered vehicles has blurred the standard characteristics associated with electrochemical storage systems. Presently, electrochemical systems comprised of mechanically rechargeable primary batteries, secondary batteries, and fuel cells are candidates for electrochemical propulsion sources. While important advances in energy and power density continue for nonaqueous and molten electrolytes, aqueous electrolyte batteries often have an advantage in simplicity, conductivity, cost effectiveness, and environmental impact. Systems coupling aluminum anodes and aqueous electrolytes have been investigated. These systems include: aluminum/silver oxide, aluminum/manganese dioxide, aluminum air, aluminum/hydrogen peroxide aqueous batteries, and the recently introduced aluminum/ferricyanide and aluminum sulfur aqueous batteries. Conventional aqueous systems such as the nickel cadmium and lead-acid batteries are characterized by their relatively low energy densities and adverse environmental impact. Other systems have substantially higher theoretical energy capacities. While aluminum-silver oxide has demonstrated the highest steady-state power density, its high cost is an impediment for widespread utilization for electric propulsion.

Hydrogen bond breaking in aqueous solutions near the critical point

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2001-01-01

The nature of water-anion bonding is examined using X-ray absorption fine structure spectroscopy on a 1mZnBr2/6m NaBr aqueous solution, to near critical conditions. Analyses show that upon heating the solution from 25??C to 500??C, a 63% reduction of waters occurs in the solvation shell of ZnBr42-, which is the predominant complex at all pressure-temperature conditions investigated. A similar reduction in the hydration shell of waters in the Br- aqua ion was found. Our results indicate that the water-anion and water-water bond breaking mechanisms occurring at high temperatures are essentially the same. This is consistent with the hydration waters being weakly hydrogen bonded to halide anions in electrolyte solutions. ?? 2001 Elsevier Science B.V.

The thermodynamic parameters of the step dissociation of L-phenylalanyl in aqueous solution

NASA Astrophysics Data System (ADS)

Kochergina, L. A.; Emel'Yanov, A. V.; Krutova, O. N.; Gorboletova, G. G.

2007-10-01

The heats of interaction of L-phenylalanine with solutions of nitric acid and potassium and lithium hydroxides were determined calorimetrically at 288.15, 298.15, and 308.15 K and solution ionic strengths of 0.5, 0.75, and 1.0 in the presence of LiNO3 and KNO3. The standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°, and Δ C {/p °} of acid-base interactions in aqueous solutions of L-phenylalanine were calculated. The influence of the concentration of background electrolytes and temperature on the heats of dissociation of L-phenylalanine was considered. A comparative analysis of the standard thermodynamic characteristics of step dissociation of L-phenylalanine and alanine was performed in terms of the modern concepts of the structure and physicochemical properties of these compounds and their solutions.

Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.

PubMed

Favaro, Marco; Abdi, Fatwa F; Lamers, Marlene; Crumlin, Ethan J; Liu, Zhi; van de Krol, Roel; Starr, David E

2018-01-18

Bismuth vanadate has recently drawn significant research attention as a light-absorbing photoanode due to its performance for photoelectrochemical water splitting. In this study, we use in situ ambient pressure X-ray photoelectron spectroscopy with "tender" X-rays (4.0 keV) to investigate a polycrystalline bismuth vanadate (BiVO 4 ) electrode in contact with an aqueous potassium phosphate (KPi) solution at open circuit potential under both dark and light conditions. This is facilitated by the creation of a 25 to 30 nm thick electrolyte layer using the "dip-and-pull" method. We observe that under illumination bismuth phosphate forms on the BiVO 4 surface leading to an increase of the surface negative charge. The bismuth phosphate layer may act to passivate surface states observed in photoelectrochemical measurements. The repulsive interaction between the negatively charged surface under illumination and the phosphate ions in solution causes a shift in the distribution of ions in the thin aqueous electrolyte film, which is observed as an increase in their photoelectron signals. Interestingly, we find that such changes at the BiVO 4 /KPi electrolyte interface are reversible upon returning to dark conditions. By measuring the oxygen 1s photoelectron peak intensities from the phosphate ions and liquid water as a function of time under dark and light conditions, we determine the time scales for the forward and reverse reactions. Our results provide direct evidence for light-induced chemical modification of the BiVO 4 /KPi electrolyte interface.

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

Effect of electrolytes on bubble coalescence in columns observed with visualization techniques.

PubMed

Aguilera, María Eugenia; Ojeda, Antonieta; Rondón, Carolina; López De Ramos, Aura

2002-10-01

Bubble coalescence and the effect of electrolytes on this phenomenon have been previously studied. This interfacial phenomenon has attracted attention for reactor design/operation and enhanced oil recovery. Predicting bubble coalescence may help prevent low yields in reactors and predict crude oil recovery. Because of the importance of bubble coalescence, the objectives of this work were to improve the accuracy of measuring the percentage of coalescing bubbles and to observe the interfacial gas-liquid behavior. An experimental setup was designed and constructed. Bubble interactions were monitored with a visualization setup. The percentage of air bubble coalescence was 100% in distilled water, about 50% in 0.1 M sodium chloride (NaCl) aqueous solution, and 0% in 0.145 M NaCl aqueous solution. A reduction of the contact gas-liquid area was observed in distillate water. The volume of the resulting bubble was the sum of the original bubble volumes. Repulsion of bubbles was observed in NaCl solutions exceeding 0.07 M. The percentage of bubble coalescence diminishes as the concentration of NaCl chloride increases. High-speed video recording is an accurate technique to measure the percentage of bubble coalescence, and represents an important advance in gas-liquid interfacial studies.

Treated Carbon Nanofibers for Storing Energy in Aqueous KOH

NASA Technical Reports Server (NTRS)

Firsich, David W.

2004-01-01

A surface treatment has been found to enhance the performances of carbon nanofibers as electrode materials for electrochemical capacitors in which aqueous solutions of potassium hydroxide are used as the electrolytes. In the treatment, sulfonic acid groups are attached to edge plane sites on carbon atoms. The treatment is applicable to a variety of carbon nanofibers, including fibrils and both single- and multiple-wall nanotubes. The reason for choosing nanofibers over powders and other forms of carbon is that nanofibers offer greater power features. In previous research, it was found that the surface treatment of carbon nanofibers increased energy-storage densities in the presence of acid electrolytes. Now, it has been found that the same treatment increases energy-storage densities of carbon nanofibers in the presence of alkaline electrolytes when the carbon is paired with a NiOOH electrode. This beneficial effect varies depending on the variety of carbon substrate to which it is applied. It has been conjectured that the sulfonic acid groups, which exist in a deprotonated state in aqueous KOH solutions, undergo reversible electro-chemical reactions that are responsible for the observed increases in energystorage capacities. The increases can be considerable: For example, in one case, nanofibers exhibited a specific capacitance of 34 Farads per gram before treatment and 172 Farads per gram (an increase of about 400 percent) after treatment. The most promising application of this development appears to lie in hybrid capacitors, which are devices designed primarily for storing energy. These devices are designed to be capable of (1) discharge at rates greater than those of batteries and (2) storing energy at densities approaching those of batteries. A hybrid capacitor includes one electrode like that of a battery and one electrode like that of an electrochemical capacitor. For example, a hybrid capacitor could contain a potassium hydroxide solution as the electrolyte, a carbon capacitor electrode, and a nickel hydroxide battery electrode. By making the capacitor electrode of treated carbon nanofibers instead of another carbon material, one could obtain greater energy-storage capacity.

Pt Catalyst Degradation in Aqueous and Fuel Cell Environments studied via In-Operando Anomalous Small-Angle X-ray Scattering

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

Gilbert, James A.; Kariuki, Nancy N.; Wang, Xiaoping

2015-08-01

The evolution of Pt nanoparticle cathode electrocatalyst size distribution in a polymer electrolyte membrane fuel cell (PEMFC) was followed during accelerated stress tests using in-operando anomalous small-angle X-ray scattering (ASAXS). This evolution was compared to that observed in an aqueous electrolyte environment using stagnant electrolyte, flowing electrolyte, and flowing electrolyte at elevated temperature to reveal the different degradation trends in the PEMFC and aqueous environments and to determine the relevance of aqueous measurements to the stability of Pt nanoparticle catalyst in the fuel cell environment. The observed changes in the particle size distributions (PSDs) were analyzed to elucidate the extentmore » and mechanisms of particle growth and corresponding mass and active surface area losses in the different environments. These losses indicate a Pt nanoparticle surface area loss mechanism controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. Based on the geometric surface area loss, mass loss, and mean particle size increase trends, the aqueous environment best reflecting the fuel cell environment was found to be one in which the electrolyte is flowing rather than stagnant. Pt nanoparticle surface area loss resulting from potential cycling can be inhibited by reducing the number of particles smaller than a critical particle diameter (CPD), which was found to be similar to 3.5 to similar to 4 nm, with the CPD dependent on both the cycling protocol (square wave vs triangle wave) and the catalyst environment (fuel cell, aqueous stagnant, aqueous flowing electrolyte, or elevated temperature flowing electrolyte)« less

The decisive role of free water in determining homogenous ice nucleation behavior of aqueous solutions

PubMed Central

Wang, Qiang; Zhao, Lishan; Li, Chenxi; Cao, Zexian

2016-01-01

It is a challenging issue to quantitatively characterize how the solute and pressure affect the homogeneous ice nucleation in a supercooled solution. By measuring the glass transition behavior of solutions, a universal feature of water-content dependence of glass transition temperature is recognized, which can be used to quantify hydration water in solutions. The amount of free water can then be determined for water-rich solutions, whose mass fraction, Xf, is found to serve as a universal relevant parameter for characterizing the homogeneous ice nucleation temperature, the meting temperature of primary ice, and even the water activity of solutions of electrolytes and smaller organic molecules. Moreover, the effects of hydrated solute and pressure on ice nucleation is comparable, and the pressure, when properly scaled, can be incorporated into the universal parameter Xf. These results help establish the decisive role of free water in determining ice nucleation and other relevant properties of aqueous solutions. PMID:27225427

Zinc-based electrolyte compositions, and related electrochemical processes and articles

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

Kniajanski, Sergei; Soloveichik, Grigorii Lev

An aqueous electrolyte composition is described, including a zinc salt based on zinc acetate or zinc glocolate. The saturation concentration of zinc in the electrolyte composition is in the range of about 2.5M to about 3.5M. The composition also contains at least one salt of a monovalent cation. The molar ratio of zinc to the monovalent cation is about 1:2. An aqueous zinc electroplating bath, containing the aqueous electrolyte composition, is also disclosed, along with a method for the electrochemical deposition of zinc onto a substrate surface, using the electroplating bath. Related flow batteries are also described, including a catholyte,more » as well as an anolyte based on the aqueous electrolyte composition, with a membrane between the catholyte and the anolyte.« less

Capacitance‐Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation

PubMed Central

Lamb, Katie J.; Dowsett, Mark R.; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D.

2017-01-01

Abstract An electrochemical cell comprising a novel dual‐component graphite and Earth‐crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero‐carbon energy source. PMID:29171724

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Coupling between electrolyte and organic semiconductor in electrolyte-gated organic field effect transistors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Biscarini, Fabio; Di Lauro, Michele; Berto, Marcello; Bortolotti, Carlo A.; Geerts, Yves H.; Vuillaume, Dominique

2016-11-01

Organic field effect transistors (OFET) operated in aqueous environments are emerging as ultra-sensitive biosensors and transducers of electrical and electrochemical signals from a biological environment. Their applications range from detection of biomarkers in bodily fluids to implants for bidirectional communication with the central nervous system. They can be used in diagnostics, advanced treatments and theranostics. Several OFET layouts have been demonstrated to be effective in aqueous operations, which are distinguished either by their architecture or by the respective mechanism of doping by the ions in the electrolyte solution. In this work we discuss the unification of the seemingly different architectures, such as electrolyte-gated OFET (EGOFET), organic electrochemical transistor (OECT) and dual-gate ion-sensing FET. We first demonstrate that these architectures give rise to the frequency-dependent response of a synapstor (synapse-like transistor), with enhanced or depressed modulation of the output current depending on the frequency of the time-dependent gate voltage. This behavior that was reported for OFETs with embedded metal nanoparticles shows the existence of a capacitive coupling through an equivalent network of RC elements. Upon the systematic change of ions in the electrolyte and the morphology of the charge transport layer, we show how the time scale of the synapstor is changed. We finally show how the substrate plays effectively the role of a second bottom gate, whose potential is actually fixed by the pH/composition of the electrolyte and the gate voltage applied.

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

NASA Astrophysics Data System (ADS)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

Towards an all-copper redox flow battery based on a copper-containing ionic liquid.

PubMed

Schaltin, Stijn; Li, Yun; Brooks, Neil R; Sniekers, Jeroen; Vankelecom, Ivo F J; Binnemans, Koen; Fransaer, Jan

2016-01-07

The first redox flow battery (RFB), based on the all-copper liquid metal salt [Cu(MeCN)4][Tf2N], is presented. Liquid metal salts (LMS) are a new type of ionic liquid that functions both as solvent and electrolyte. Non-aqueous electrolytes have advantages over water-based solutions, such as a larger electrochemical window and large thermal stability. The proof-of-concept is given that LMSs can be used as the electrolyte in RFBs. The main advantage of [Cu(MeCN)4][Tf2N] is the high copper concentration, and thus high charge and energy densities of 300 kC l(-1) and 75 W h l(-1) respectively, since the copper(i) ions form an integral part of the electrolyte. A Coulombic efficiency up to 85% could be reached.

Electrolyte-gated transistors based on conducting polymer nanowire junction arrays.

PubMed

Alam, Maksudul M; Wang, Jun; Guo, Yaoyao; Lee, Stephanie P; Tseng, Hsian-Rong

2005-07-07

In this study, we describe the electrolyte gating and doping effects of transistors based on conducting polymer nanowire electrode junction arrays in buffered aqueous media. Conducting polymer nanowires including polyaniline, polypyrrole, and poly(ethylenedioxythiophene) were investigated. In the presence of a positive gate bias, the device exhibits a large on/off current ratio of 978 for polyaniline nanowire-based transistors; these values vary according to the acidity of the gate medium. We attribute these efficient electrolyte gating and doping effects to the electrochemically fabricated nanostructures of conducting polymer nanowires. This study demonstrates that two-terminal devices can be easily converted into three-terminal transistors by simply immersing the device into an electrolyte solution along with a gate electrode. Here, the field-induced modulation can be applied for signal amplification to enhance the device performance.

Monitoring of oxidation steps of ascorbic acid redox reaction by kinetics-sensitive voltcoulometry in unsupported and supported aqueous solutions and real samples.

PubMed

Orlický, Jozef; Gmucová, Katarína; Thurzo, Ilja; Pavlásek, Juraj

2003-04-01

Aqueous solutions of ascorbic acid in unsupported and supported aqueous solutions and real samples were studied by the kinetics-sensitive double-step voltcoulommetric method with the aim to contribute to a better understanding of its behavior in biological systems. The data obtained from measurements made on analytes prepared in the laboratory, as well as those made on real samples (some commercial orange drinks, flash of the fresh fruits) point to the redox reaction of L-ascorbic acid (L-AH2) being very sensitive to both the presence of dissolved gaseous species (O2, CO2) and the ionic strenght in the analyte. Either the dissolved gaseous species, or the higher ionic strength caused by both the presence of supporting electrolyte and increased total concentration of ascorbic acid, respectively, give birth to the degradation of L-AH2. Naturally, the highest percentage of L-AH2 was spotted in fresh fruit.

Correlation among physical and electrochemical behaviour of nanostructured electrolytic manganese dioxide from leach liquor and synthetic for aqueous asymmetric capacitor.

PubMed

Minakshi Sundaram, Manickam; Biswal, Avijit; Mitchell, David; Jones, Rob; Fernandez, Carlos

2016-02-14

An attempt has been made to correlate the differences in structural parameters, surface areas, morphology etc. with the electrochemical capacitive behaviour of the EMDs. The nanostructured electrolytic manganese dioxides (EMD) have been synthesized through electrodepositing MnO2 from two different leach liquors and a synthetic analogue thereof. The structural and chemical state was determined using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) respectively. Multiplet structure determination led to estimates of the manganese valence states present in the EMD. The EMDs have been tested in an asymmetric capacitor which we have developed. This used activated carbon as the negative electrode and the various EMDs as the positive electrode. Aqueous 2 M NaOH solution was used as the electrolyte. The capacitor achieved 1.6 V corresponding to a capacitance of ∼50 F g(-1) of the EMDs from leach liquors. The EMD derived from the synthetic solution showed an inferior capacitance of 25 F g(-1). Extended cycling (2000 cycles), showed 100% capacity retention was achieved for one EMD produced from the leach liquor derived from low-grade manganese ore/residue. This outstanding capacitor performance was correlated with the presence of a nanofibrous morphology. These findings open up the possibility of extracting a high performance EMD product from a low cost, low-grade source of manganese.

Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O

NASA Astrophysics Data System (ADS)

Pabalan, Roberto T.; Pitzer, Kenneth S.

1987-09-01

Mineral solubilities in binary and ternary electrolyte mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O are calculated to high temperatures using available thermodynamic data for solids and for aqueous electrolyte solutions. Activity and osmotic coefficients are derived from the ion-interaction model of Pitzer (1973, 1979) and co-workers, the parameters of which are evaluated from experimentally determined solution properties or from solubility data in binary and ternary mixtures. Excellent to good agreement with experimental solubilities for binary and ternary mixtures indicate that the model can be successfully used to predict mineral-solution equilibria to high temperatures. Although there are currently no theoretical forms for the temperature dependencies of the various model parameters, the solubility data in ternary mixtures can be adequately represented by constant values of the mixing term θ ij and values of ψ ijk which are either constant or have a simple temperature dependence. Since no additional parameters are needed to describe the thermodynamic properties of more complex electrolyte mixtures, the calculations can be extended to equilibrium studies relevant to natural systems. Examples of predicted solubilities are given for the quaternary system NaCl-KCl-MgCl 2-H 2O.

Optimization of electrochemical dechlorination of trichloroethylene in reducing electrolytes

PubMed Central

Mao, Xuhui; Ciblak, Ali; Baek, Kitae; Amiri, Mohammad; Loch-Caruso, Rita; Alshawabkeh, Akram N.

2012-01-01

Electrochemical dechlorination of trichloroethylene (TCE) in aqueous solution is investigated in a closed, liquid-recirculation system. The anodic reaction of cast iron generates ferrous species, creating a chemically reducing electrolyte (negative ORP value). The reduction of TCE on the cathode surface is enhanced under this reducing electrolyte because of the absence of electron competition. In the presence of the iron anode, the performances of different cathodes are compared in a recirculated electrolysis system. The copper foam shows superior capability for dechlorination of aqueous TCE. Electrolysis by cast iron anode and copper foam cathode is further optimized though a multivariable experimental design and analysis. The conductivity of the electrolyte is identified as an important factor for both final elimination efficiency (FEE) of TCE and specific energy consumption. The copper foam electrode exhibits high TCE elimination efficiency in a wide range of initial TCE concentration. Under coulostatic conditions, the optimal conditions to achieve the highest FEE are 9.525 mm thick copper foam electrode, 40 mA current and 0.042 mol L−1 Na2SO4. This novel electrolysis system is proposed to remediate groundwater contaminated by chlorinated organic solvents, or as an improved iron electrocoagulation process capable of treating the wastewater co-contaminated with chlorinated compounds. PMID:22264798

Recent Advances in High-Performance Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, S. R.; Chun, W.; Valdez, T. I.; Jeffries-Nakamura, B.; Frank, H.; Surumpudi, S.; Halpert, G.; Kosek, J.; Cropley, C.; La Conti, A. B.;

Isotherm-Based Thermodynamic Models for Solute Activities of Organic Acids with Consideration of Partial Dissociation.

PubMed

Nandy, Lucy; Ohm, Peter B; Dutcher, Cari S

2016-06-23

Organic acids make up a significant fraction of the organic mass in atmospheric aerosol particles. The calculation of gas-liquid-solid equilibrium partitioning of the organic acid is therefore critical for accurate determination of atmospheric aerosol physicochemical properties and processes such as new particle formation and activation to cloud condensation nuclei. Previously, an adsorption isotherm-based statistical thermodynamic model was developed for capturing solute concentration-activity relationships for multicomponent aqueous solutions over the entire concentration range (Dutcher et al. J. Phys. Chem. C/A 2011, 2012, 2013), with model parameters for energies of adsorption successfully related to dipole-dipole electrostatic forces in solute-solvent and solvent-solvent interactions for both electrolytes and organics (Ohm et al. J. Phys. Chem. A 2015). However, careful attention is needed for weakly dissociating semivolatile organic acids. Dicarboxylic acids, such as malonic acid and glutaric acid are treated here as a mixture of nondissociated organic solute (HA) and dissociated solute (H(+) + A(-)). It was found that the apparent dissociation was greater than that predicted by known dissociation constants alone, emphasizing the effect of dissociation on osmotic and activity coefficient predictions. To avoid additional parametrization from the mixture approach, an expression was used to relate the Debye-Hückel hard-core collision diameter to the adjustable solute-solvent intermolecular distance. An improved reference state treatment for electrolyte-organic aqueous mixtures, such as that observed here with partial dissociation, has also been proposed. This work results in predictive correlations for estimation of organic acid and water activities for which there is little or no activity data.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

PubMed

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Hydrogen evolution using palladium sulfide (PdS) nanocorals as photoanodes in aqueous solution.

PubMed

Barawi, M; Ferrer, I J; Ares, J R; Sánchez, C

2014-11-26

Palladium sulfide (PdS) nanostructures are proposed to be used as photoanodes in photoelectrochemical cells (PECs) for hydrogen evolution due to their adequate transport and optical properties shown in previous works. Here, a complete morphological and electrochemical characterization of PdS films has been performed by different techniques. PdS flatband potential (Vfb=-0.65±0.05 V vs NHE) was determined by electrochemical impedance spectroscopy measurements in aqueous Na2SO3 electrolyte, providing a description of the energy levels scheme at the electrolyte-semiconductor interface. This energy levels scheme confirms PdS as a compound able to photogenerate hydrogen in a PEC. At last, photogenerated hydrogen rates are measured continuously by mass spectrometry as a function of the external bias potential under illumination, reaching values up to 4.4 μmolH2/h at 0.3 V vs Ag/AgCl.

Improvement of the electrochemical properties via poly(3,4-ethylenedioxythiophene) oriented micro/nanorods

NASA Astrophysics Data System (ADS)

Li, Yu; Wang, Bichen; Chen, Huimin; Feng, Wei

Arrays of oriented poly(3,4-ethylenedioxythiophene) (PEDOT) micro/nanorods are synthesized by electrochemical galvanostatic method at the current density of 1 mA cm -2 in the cetyltrimethylammonium bromide (CTAB) aqueous solution whose pH value is 1. The CTAB is used both as the surfactant and the supporting salt in the electrolyte solution. The electrochemical properties of PEDOT films are characterized by cyclic voltammetry and galvanostatic charge/discharge techniques, which indicate that the arrays of oriented PEDOT micro/nanorods can be applied as the electrode materials of supercapacitors. In addition, the cycling performance of PEDOT micro/nanorods is much better than that of traditional PEDOT particles. The effects of the concentration of CTAB, the current density, and pH value of electrolyte solutions on the morphologies and electrochemical properties of PEDOT films are investigated. The mechanism of different morphologies formation is discussed in this study as well.

Microbubble Fabrication of Concave-porosity PDMS Beads

PubMed Central

Bertram, John R.; Nee, Matthew J.

2015-01-01

Microbubble fabrication (by use of a fine emulsion) provides a means of increasing the surface-area-to-volume (SAV) ratio of polymer materials, which is particularly useful for separations applications. Porous polydimethylsiloxane (PDMS) beads can be produced by heat-curing such an emulsion, allowing the interface between the aqueous and aliphatic phases to mold the morphology of the polymer. In the procedures described here, both polymer and crosslinker (triethoxysilane) are sonicated together in a cold-bath sonicator. Following a period of cross-linking, emulsions are added dropwise to a hot surfactant solution, allowing the aqueous phase of the emulsion to separate, and forming porous polymer beads. We demonstrate that this method can be tuned, and the SAV ratio optimized, by adjusting the electrolyte content of the aqueous phase in the emulsion. Beads produced in this way are imaged with scanning electron microscopy, and representative SAV ratios are determined using Brunauer–Emmett–Teller (BET) analysis. Considerable variability with the electrolyte identity is observed, but the general trend is consistent: there is a maximum in SAV obtained at a specific concentration, after which porosity decreases markedly. PMID:26709997

Successful Stabilization of Graphene Oxide in Electrolyte Solutions: Enhancement of Bio-functionalization and Cellular Uptake

PubMed Central

Hong, Bong Jin; Compton, Owen C.; An, Zhi; Eryzazici, Ibrahim; Nguyen, SonBinh T.

2013-01-01

Aqueous dispersions of graphene oxide are inherently unstable in the presence of electrolytes, which screen the electrostatic surface charge on these nanosheets and induce irreversible aggregation. Two complementary strategies, utilizing either electrostatic or steric stabilization, have been developed to enhance the stability of graphene oxide in electrolyte solutions, allowing it to stay dispersed in cell culture media and serum. The electrostatic stabilization approach entails further oxidation of graphene oxide to low C/O ratio (~1.03) and increases ionic tolerance of these nanosheets. The steric stabilization technique employs an amphiphilic block copolymer that serves as a non-covalently bound surfactant to minimize the aggregate-induced nanosheets-nanosheet interactions. Both strategies can stabilize graphene oxide nanosheets with large dimensions (>300 nm) in biological media, allowing for an enhancement of >250% in the bioconjugation efficiency of streptavidin in comparison to untreated nanosheets. Notably, both strategies allow the stabilized nanosheets to be readily uptake by cells, demonstrating their excellent performance as potential drug delivery vehicles. PMID:22017285

Recovery of valuable elements from spent Li-batteries.

PubMed

Paulino, Jéssica Frontino; Busnardo, Natália Giovanini; Afonso, Julio Carlos

2008-02-11

This work examines two recycling processes for spent Li/MnO(2) and Li-ion batteries. The anode, cathode and electrolyte (LiPF(6)) were submitted to one of the following procedures: (a) calcination at 500 degrees C (5h) followed by solvent extraction to recover lithium salts (fluoride, phosphate) in good yield (90 wt%). The residual solid was treated with H(2)SO(4) containing H(2)O(2) and on evaporation gave high purity grade cobalt or manganese sulfate; (b) fusion with KHSO(4) (500 degrees C, 5h). The resulting aqueous solution was added dropwise to a solution of NaOH, giving cobalt or manganese as impure precipitate. Addition of KF precipitated high purity grade LiF in moderate yield (50 wt%). The final aqueous solution on treatment with calcium sulfate precipitated the corresponding phosphate and fluoride salts.

Electrochemical system and method for electropolishing hollow metal bodies

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

Taylor, E. Jennings; Inman, Maria E.; Hall, Timothy

A method and system for electrochemically machining a hollow body of a metal or a metal alloy. An electrode is positioned within a hollow body including a metal or metal alloy, where the hollow body has a variable internal diameter. The hollow body is oriented vertically, with the electrode oriented vertically therein. The hollow body is at least partially filled with an aqueous, acidic electrolyte solution, the electrolyte solution being devoid of hydrofluoric acid and having a viscosity less than 15 cP. An electric current is passed between the hollow body and the electrode, where the electric current includes amore » plurality of anodic pulses and a plurality of cathodic pulses, and where the cathodic pulses are interposed between at least some of the anodic pulses.« less

High voltage rechargeable magnesium batteries having a non-aqueous electrolyte

DOEpatents

Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E.; Hwang, Jaehee

2016-03-22

A rechargable magnesium battery having an non-aqueous electrolyte is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

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

Ruther, Rose E.; Sun, Che -Nan; Holliday, Adam

A simple electrolyte consisting of NaPF 6 salt in 1,2-dimethoxyethane (DME) can extend the voltage window of electric double-layer capacitors (EDLCs) to >3.5 V. DME does not passivate carbon electrodes at very negative potentials (near Na/Na +), extending the practical voltage window by about 1.0 V compared to standard, non-aqueous electrolytes based on acetonitrile. The voltage window is demonstrated in two- and three-electrode cells using a combination of electrochemical impedance spectroscopy (EIS), charge-discharge cycling, and measurements of leakage current. DME-based electrolytes cannot match the high conductivity of acetonitrile solutions, but they can satisfy applications that demand high energy density atmore » moderate power. The conductivity of NaPF 6 in DME is comparable to commercial lithium-ion battery electrolytes and superior to most ionic liquids. Lastly, factors that limit the voltage window and EDLC energy density are discussed, and strategies to further boost energy density are proposed.« less

Synthesis and Characterization of Cellulose-Based Hydrogels to Be Used as Gel Electrolytes

PubMed Central

Navarra, Maria Assunta; Dal Bosco, Chiara; Serra Moreno, Judith; Vitucci, Francesco Maria; Paolone, Annalisa; Panero, Stefania

2015-01-01

Cellulose-based hydrogels, obtained by tuned, low-cost synthetic routes, are proposed as convenient gel electrolyte membranes. Hydrogels have been prepared from different types of cellulose by optimized solubilization and crosslinking steps. The obtained gel membranes have been characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mechanical tests in order to investigate the crosslinking occurrence and modifications of cellulose resulting from the synthetic process, morphology of the hydrogels, their thermal stability, and viscoelastic-extensional properties, respectively. Hydrogels liquid uptake capability and ionic conductivity, derived from absorption of aqueous electrolytic solutions, have been evaluated, to assess the successful applicability of the proposed membranes as gel electrolytes for electrochemical devices. To this purpose, the redox behavior of electroactive species entrapped into the hydrogels has been investigated by cyclic voltammetry tests, revealing very high reversibility and ion diffusivity. PMID:26633528

Non-aqueous electrolytes for isotachophoresis of weak bases and its application to the comprehensive preconcentration of the 20 proteinogenic amino acids in column-coupling ITP/CE-MS.

PubMed

Kler, Pablo A; Huhn, Carolin

2014-11-01

Isotachophoresis (ITP) has long been used alone but also as a preconcentration technique for capillary electrophoresis (CE). Unfortunately, up to now, its application is restricted to relatively strong acids and bases as either the degree of (de)protonation is too low or the water dissociation is too high, evoking zone electrophoresis. With the comprehensive ITP analysis of all 20 proteinogenic amino acids as model analytes, we, here, show that non-aqueous ITP using dimethylsulfoxide as a solvent solves this ITP shortcoming. Dimethylsulfoxide changes the pH regime of analytes and electrolytes but, more importantly, strongly reduces the proton mobility by prohibiting hydrogen bonds and thus, the so-called Zundel-Eigen-Zundel electrical conduction mechanism of flipping hydrogen bonds. The effects are demonstrated in an electrolyte system with taurine or H(+) as terminator, and imidazole as leader together with strong acids such as oxalic and even trifluoroacetic acid as counterions, both impossible to use in aqueous solution. Mass spectrometric as well as capacitively coupled contactless conductivity detection (C(4)D) are used to follow the ITP processes. To demonstrate the preconcentration capabilities of ITP in a two-dimensional set-up, we, here, also demonstrate that our non-aqueous ITP method can be combined with capillary electrophoresis-mass spectrometry in a column-coupling system using a hybrid approach of capillaries coupled to a microfluidic interface. For this, C(4)D was optimized for on-chip detection with the electrodes aligned on top of a thin glass lid of the microfluidic chip.

Stable electrolyte for high voltage electrochemical double-layer capacitors

DOE PAGES

Ruther, Rose E.; Sun, Che -Nan; Holliday, Adam; ...

2016-12-28

A simple electrolyte consisting of NaPF 6 salt in 1,2-dimethoxyethane (DME) can extend the voltage window of electric double-layer capacitors (EDLCs) to >3.5 V. DME does not passivate carbon electrodes at very negative potentials (near Na/Na +), extending the practical voltage window by about 1.0 V compared to standard, non-aqueous electrolytes based on acetonitrile. The voltage window is demonstrated in two- and three-electrode cells using a combination of electrochemical impedance spectroscopy (EIS), charge-discharge cycling, and measurements of leakage current. DME-based electrolytes cannot match the high conductivity of acetonitrile solutions, but they can satisfy applications that demand high energy density atmore » moderate power. The conductivity of NaPF 6 in DME is comparable to commercial lithium-ion battery electrolytes and superior to most ionic liquids. Lastly, factors that limit the voltage window and EDLC energy density are discussed, and strategies to further boost energy density are proposed.« less

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

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

Self-association of analgesics in aqueous solution: micellar properties of dextropropoxyphene hydrochloride and methadone hydrochloride.

PubMed

Attwood, D; Tolley, J A

1980-08-01

The solution properties of several analgesics including dextropropoxyphene hydrochloride, methadone hydrochloride, dextromoramide acid tartrate and dipipanone hydrochloride have been examined using light scattering, conductivity, vapour pressure osmometry and surface tension techniques. A micellar pattern of association was established for dextropropoxyphene hydrochloride and methadone hydrochloride and critical micelle concentrations and aggregation numbers are reported. The hydrophobic contribution to the free energy of micellization of dextropropoxyphene was determined from measurement of the critical micelle concentration in the presence of added electrolyte.

Corrosion Mechanisms and Behavior of a P-130X GR/6063 Al Composite in Aqueous Environments

DTIC Science & Technology

1990-09-01

form sulfuric and sulfurous acids . Of these, sulfurous acid is the most serious corrosive material and can exist in a variety of concentrations...performed on the composite in 3.5% sodium chloride and 5.0% >dium sulfate solutions. The effects of pH, the presence of sulfite ions, various heat...sodium sulfate solutions. The effects of pH, the presence of sulfite ions, various heat treatments, and electrolyte aeration were investigated. Some tests

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

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

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

A Cheap, Semiquantitative Hand-Held Conductivity Tester.

ERIC Educational Resources Information Center

Zawacky, Susan K. S.

1995-01-01

Describes a design for a hand-held conductivity tester powered by a 9V battery that gives semi-quantitative results for aqueous electrolyte solutions of concentrations ranging from 0.001 M to 0.1 M. The tester uses a bar-graph LED driven by an LM3914 integrated circuit to indicate the level of conductivity. A list of parts, procedures, and results…

Electrolytic Transformation of Hexahydro-1,3,5-Trinitro-1,3,5-Triazine (RDX) and 2,4,6-Trinitrotoluene (TNT) in Aqueous Solutions

DTIC Science & Technology

2005-08-01

several years (Bunce et al. 1997; de Lima Leite et al. 2003; Panizza and Cerisola 2004). Treatment is achieved by either oxidation (anodic) or...and mixed anaerobic cultures," Environ. Sci. Technol. 35, 4341-4346. Panizza , M., and Cerisola, G. (2004). "Influence of anode material on the

Studies on the effect of acid treated TiO{sub 2} on the electrical and tensile properties of hexanoyl chitosan-polystyrene-LiCF{sub 3}SO{sub 3} composite polymer electrolytes

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

Hanif, Nur Shazlinda Muhammad; Shahril, Nur Syuhada Mohd; Azmar, Amisha

2015-08-28

Composite polymer electrolytes (CPEs) comprised of hexanoyl chitosan:polystyrene (90:10) blend, lithium triflouromethanesulfonate (LiCF{sub 3}SO{sub 3}) salt and titanium oxide (TiO{sub 2}) filler were prepared by solution casting technique. The TiO{sub 2} fillers were treated with 2% sulphuric acid (H{sub 2}SO{sub 4}) aqueous solution. The effect of acid treated TiO{sub 2} on the electrical and tensile properties of the electrolytes were investigated. Acid treated TiO{sub 2} decreased the electrolyte conductivity. Both the dielectric constant and dielectric loss decrease with increasing frequency and increases with increasing temperature. Relaxation times for ionic carriers were extracted from the loss tangent maximum peak at variousmore » temperatures. A distribution of relaxation time implied the non-Debye response. At all frequencies, ac conductivity increases with increasing temperature. An enhancement in the Young’s modulus was observed with the addition of TiO{sub 2}. The Young’s modulus increases with increasing TiO{sub 2} content. This is discussed using the percolation concept.« less

Hybrid capacitor with activated carbon electrode, Ni(OH) 2 electrode and polymer hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Nohara, Shinji; Asahina, Toshihide; Wada, Hajime; Furukawa, Naoji; Inoue, Hiroshi; Sugoh, Nozomu; Iwasaki, Hideharu; Iwakura, Chiaki

A new hybrid capacitor (HC) cell was assembled using an activated carbon (AC) negative electrode, an Ni(OH) 2 positive electrode and a polymer hydrogel electrolyte prepared from crosslinked potassium poly(acrylate) (PAAK) and KOH aqueous solution. The HC cell was characterized compared with an electric double layer capacitor (EDLC) using two AC electrodes and the polymer hydrogel electrolyte. It was found that the HC cell successfully worked in the larger voltage range and exhibited ca. 2.4 times higher capacitance than the EDLC cell. High-rate dischargeability of the HC cell was also superior to that of the EDLC cell. These improved characteristics strongly suggest that the HC cell can be a promising system of capacitors with high energy and power densities.

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.

PubMed

Mazzini, Virginia; Craig, Vincent S J

2017-10-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity.

Performance of Carbon/Polytetrafluoroethylene (PTFE) Air Cathodes from pH 0 to 14 for Li-Air Batteries

DTIC Science & Technology

2007-12-01

aqueous and aqueous electrolytes are kept separate by a non-electronically conducting ceramic membrane impervious to water, but with a high ionic...thought of as being solvated by the ceramic membrane as it passes from non-aqueous to aqueous electrolyte. The half-cell reaction at the lithium...overall charge in the reaction, positive lithium ions flow through an ionically conducting ceramic membrane from the non-aqueous anode compartment to

Interfacial water on crystalline silica: a comparative molecular dynamics simulation study

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

Ho, Tuan A.; Argyris, Dimitrios; Papavassiliou, Dimitrios V.

2011-03-03

All-atom molecular dynamics simulations were conducted to study the dynamics of aqueous electrolyte solutions confined in slit-shaped silica nanopores of various degrees of protonation. Five degrees of protonation were prepared by randomly removing surface hydrogen atoms from fully protonated crystalline silica surfaces. Aqueous electrolyte solutions containing NaCl or CsCl salt were simulated at ambient conditions. In all cases, the ionic concentration was 1 M. The results were quantified in terms of atomic density distributions within the pores, and the self-diffusion coefficient along the direction parallel to the pore surface. We found evidence for ion-specific properties that depend on ion surface,more » water ion, and only in some cases ion ion correlations. The degree of protonation strongly affects the structure, distribution, and the dynamic behavior of confined water and electrolytes. Cl ions adsorb on the surface at large degrees of protonation, and their behavior does not depend significantly on the cation type (either Na+ or Cs+ ions are present in the systems considered). The cations show significant ion-specific behavior. Na+ ions occupy different positions within the pore as the degree of protonation changes, while Cs+ ions mainly remain near the pore center at all conditions considered. For a given degree of protonation, the planar self-diffusion coefficient of Cs+ is always greater than that of Na+ ions. The results are useful for better understanding transport under confinement, including brine behavior in the subsurface, with important applications such as environmental remediation.« less

An effective way to reduce water absorption to terahertz

NASA Astrophysics Data System (ADS)

Wu, Yaxiong; Su, Bo; He, Jingsuo; Zhang, Cong; Zhang, Hongfei; Zhang, Shengbo; Zhang, Cunlin

2018-01-01

Since many vibrations and rotational levels of biomolecules fall within the THz band, THz spectroscopy can be used to identify biological samples. In addition, most biomolecules need to maintain their biological activity in a liquid environment, but water as polar substance has strong absorption to the THz wave. Thus, it is difficult to detect the sample information in aqueous solution using THz wave. In order to prevent the information of biological samples were masked in the solution, many research methods were used to explore how to reduce the water absorption of terahertz. In this paper, we have developed a real-time chemical methodology through transmission Terahertz time-domain spectroscopy (THz-TDS) system. The material of Zeonor 1020r is used as substrate and cover plate, and PDMS as channel interlayer. The transmission of the empty microfluidic chip is more than 80% in the range of 0.2-2.6 THz by THz-TDS system. Then, experiments were carried out using chips, which were filled with different volumes of 1, 2- propanediol, and it has been proved that the microfluidic chip could reduce the water absorption of terahertz. Finally, in order to further explore the reduction of terahertz to water absorption, we inject different concentrations of electrolyte to the chip. The results show that with the addition of different electrolytes, terahertz transmission line has evident changes. It can be taken into account that the electrolyte has different effects about the hydrogen bonds in the aqueous solution. Some of them can promote water molecules clusters, while others destroy them. Based on the basis of microfluidic chip, the discovery of this phenomenon can provide a way that reduces water absorption of terahertz. This work has laid a solid foundation for the subsequent study in reducing water absorption of terahertz.

Electrolyte effects in a model of proton discharge on charged electrodes

NASA Astrophysics Data System (ADS)

Wiebe, Johannes; Kravchenko, Kateryna; Spohr, Eckhard

2015-01-01

We report results on the influence of NaCl electrolyte dissolved in water on proton discharge reactions from aqueous solution to charged platinum electrodes. We have extended a recently developed combined proton transfer/proton discharge model on the basis of empirical valence bond theory to include NaCl solutions with several different concentrations of cations and anions, both stoichiometric (1:1) compositions and non-stoichiometric ones with an excess of cations. The latter solutions partially screen the electrostatic potential from the surface charge of the negatively charged electrode. 500-1000 trajectories of a discharging proton were integrated by molecular dynamics simulations until discharge occurred, or for at most 1.5 ns. The results show a strong dependence on ionic strength, but only a weak dependence on the screening behavior, when comparing stoichiometric and non-stoichiometric solutions. Overall, the Na+ cations exert a more dominant effect on the discharge reaction, which we argue is likely due to the very rigid arrangements of the cations on the negatively polarized electrode surface. Thus, our model predicts, for the given and very high negative surface charge densities, the fastest discharge reaction for pure water, but obviously cannot take into account the fact that such high charge densities are even more out of reach experimentally than for higher electrolyte concentrations.

Solvation thermodynamics of L-cystine, L-tyrosine, and L-leucine in aqueous-electrolyte media

NASA Astrophysics Data System (ADS)

Roy, Sanjay; Guin, Partha Sarathi; Mahali, Kalachand; Dolui, Bijoy Krishna

2017-12-01

Solubilities of L-cystine, L-tyrosine, and L-leucine in aqueous NaCl media at 298.15 K have been studied. Indispensable and related solvent parameters such as molar mass, molar volume, etc., were also determined. The results are used to evaluate the standard transfer Gibbs free energy, cavity forming enthalpy of transfer, cavity forming transfer Gibbs free energy and dipole-dipole interaction effects during the course of solvation. Various weak interactions involving solute-solvent or solvent-solvent molecules were characterized in order to find their role on the solvation of these amino acids.

A Tandem Microscopic-Electrochemical Examination of A Charge-Induced Surface Phase Sequence: Ordered Au(110) in Aqueous Iodide Electrolytes as Probed by Potentiodynamic Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

and Rh(lll)9-12 by STM, and halides on Au(lll) by SXRS. 1 3 ’ 1 4 For several of these systems, especially anion adsorption on gold , the adsorbate...index faces of gold in aqueous solution by means of in- situ STM combined with conventional electrochemical methods. The value of the electrochemical...structure and conversion dynamics. A related description of the Au(lO0)-I- system, along with a comparison with the behavior of the other two low-index gold

Influence of electrochemical potential on the displacement of aqueous electrolyte from a copper surface by oil

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

Kendig, M.W.; Fadner, T.A.

1985-02-01

The forces responsible for the meniscus formed during the dynamic displacement of a 0.1 M H/sub 3/BO/sub 3/ + 0.5 M NaClO/sub 4/ solution by oil from a copper surface depend on the electrochemical potential of the copper and on an active component in the oil. For a nonpolar mineral oil containing oleic acid, a negative potential applied to copper produces hydrophilic behavior of the copper surface in the aqueous phase. This result is attribute largely to electrochemical destabilization of metallic soaps and possibly to electroosmotic transport.

Specific ion effects on membrane potential and the permselectivity of ion exchange membranes.

PubMed

Geise, Geoffrey M; Cassady, Harrison J; Paul, Donald R; Logan, Bruce E; Hickner, Michael A

2014-10-21

Membrane potential and permselectivity are critical parameters for a variety of electrochemically-driven separation and energy technologies. An electric potential is developed when a membrane separates electrolyte solutions of different concentrations, and a permselective membrane allows specific species to be transported while restricting the passage of other species. Ion exchange membranes are commonly used in applications that require advanced ionic electrolytes and span technologies such as alkaline batteries to ammonium bicarbonate reverse electrodialysis, but membranes are often only characterized in sodium chloride solutions. Our goal in this work was to better understand membrane behaviour in aqueous ammonium bicarbonate, which is of interest for closed-loop energy generation processes. Here we characterized the permselectivity of four commercial ion exchange membranes in aqueous solutions of sodium chloride, ammonium chloride, sodium bicarbonate, and ammonium bicarbonate. This stepwise approach, using four different ions in aqueous solution, was used to better understand how these specific ions affect ion transport in ion exchange membranes. Characterization of cation and anion exchange membrane permselectivity, using these ions, is discussed from the perspective of the difference in the physical chemistry of the hydrated ions, along with an accompanying re-derivation and examination of the basic equations that describe membrane potential. In general, permselectivity was highest in sodium chloride and lowest in ammonium bicarbonate solutions, and the nature of both the counter- and co-ions appeared to influence measured permselectivity. The counter-ion type influences the binding affinity between counter-ions and polymer fixed charge groups, and higher binding affinity between fixed charge sites and counter-ions within the membrane decreases the effective membrane charge density. As a result permselectivity decreases. The charge density and polarizability of the co-ions also appeared to influence permselectivity leading to ion-specific effects; co-ions that are charge dense and have low polarizability tended to result in high membrane permselectivity.

Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X{sup −}

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

Kurahashi, Naoya; Horio, Takuya; Suzuki, Toshinori, E-mail: suzuki@kuchem.kyoto-u.ac.jp

2014-05-07

The streaming potentials of liquid beams of aqueous NaCl, NaBr, and NaI solutions are measured using soft X-ray, He(I), and laser multiphoton ionization photoelectron spectroscopy. Gaseous molecules are ionized in the vicinity of liquid beams and the photoelectron energy shifts are measured as a function of the distance between the ionization point and the liquid beam. The streaming potentials change their polarity with concentration of electrolytes, from which the singular points of concentration eliminating the streaming potentials are determined. The streaming currents measured in air also vanish at these concentrations. The electron binding energies of liquid water and I{sup −},more » Br{sup −}, and Cl{sup −} anions are revisited and determined more accurately than in previous studies.« less

On the adequacy of modeling the concentration dependences of the activity coefficients for the components of solutions

NASA Astrophysics Data System (ADS)

Sergievskii, V. V.; Rudakov, A. M.

2006-11-01

An analysis of the accepted methods for calculating the activity coefficients for the components of binary aqueous solutions was performed. It was demonstrated that the use of the osmotic coefficients in auxiliary calculations decreases the accuracy of estimates of the activity coefficients. The possibility of calculating the activity coefficient of the solute from the concentration dependence of the water activity was examined. It was established that, for weak electrolytes, the interpretation of data on heterogeneous equilibria within the framework of the standard assumption that the dissociation is complete encounters serious difficulties.

Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

NASA Astrophysics Data System (ADS)

Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

2012-11-01

In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic repulsion between the multilayered polymer coils which results in breakdown of the layer.

Manipulating semiconductor colloidal stability through doping.

PubMed

Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

2014-10-10

The interface between a doped semiconductor material and electrolyte solution is of considerable fundamental interest, and is relevant to systems of practical importance. Both adjacent domains contain mobile charges, which respond to potential variations. This is exploited to design electronic and optoelectronic sensors, and other enabling semiconductor colloidal materials. We show that the charge mobility in both phases leads to a new type of interaction between semiconductor colloids suspended in aqueous electrolyte solutions. This interaction is due to the electrostatic response of the semiconductor interior to disturbances in the external field upon the approach of two particles. The electrostatic repulsion between two charged colloids is reduced from the one governed by the charged groups present at the particles surfaces. This type of interaction is unique to semiconductor particles and may have a substantial effect on the suspension dynamics and stability.

UV-Vis spectrophotometry of quinone flow battery electrolyte for in situ monitoring and improved electrochemical modeling of potential and quinhydrone formation.

PubMed

Tong, Liuchuan; Chen, Qing; Wong, Andrew A; Gómez-Bombarelli, Rafael; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

2017-12-06

Quinone-based aqueous flow batteries provide a potential opportunity for large-scale, low-cost energy storage due to their composition from earth abundant elements, high aqueous solubility, reversible redox kinetics and their chemical tunability such as reduction potential. In an operating flow battery utilizing 9,10-anthraquinone-2,7-disulfonic acid, the aggregation of an oxidized quinone and a reduced hydroquinone to form a quinhydrone dimer causes significant variations from ideal solution behavior and of optical absorption from the Beer-Lambert law. We utilize in situ UV-Vis spectrophotometry to establish (a), quinone, hydroquinone and quinhydrone molar attenuation profiles and (b), an equilibrium constant for formation of the quinhydrone dimer (K QHQ ) ∼ 80 M -1 . We use the molar optical attenuation profiles to identify the total molecular concentration and state of charge at arbitrary mixtures of quinone and hydroquinone. We report density functional theory calculations to support the quinhydrone UV-Vis measurements and to provide insight into the dimerization conformations. We instrument a quinone-bromine flow battery with a Pd-H reference electrode in order to demonstrate how complexation in both the negative (quinone) and positive (bromine) electrolytes directly impacts measured half-cell and full-cell voltages. This work shows how accounting for electrolyte complexation improves the accuracy of electrochemical modeling of flow battery electrolytes.

Removal of chromium (VI) from aqueous solution using walnut hull.

PubMed

Wang, Xue Song; Li, Zhi Zhong; Tao, Sheng Rong

2009-02-01

In this study, removal of chromium (VI) from aqueous solution by walnut hull (a local low-cost adsorbent) was studied. The extent of adsorption was investigated as a function of solution pH, contact time, adsorbent and adsorbate concentration, reaction temperature and supporting electrolyte (sodium chloride). The Cr (VI) removal was pH-dependent, reaching a maximum (97.3%) at pH 1.0. The kinetic experimental data were fitted to the first-order, modified Freundlich, intraparticle diffusion and Elovich models and the corresponding parameters were obtained. A 102.78 kJ/mol Ea (activation energy) for the reaction of chromium (VI) adsorption onto walnut indicated that the rate-limiting step in this case might be a chemically controlled process. Both the Langmuir and Freundlich isotherms were suitable for describing the biosorption of chromium (VI) onto walnut hull. The uptake of chromium (VI) per weight of adsorbent increased with increasing initial chromium (VI) concentration up to 240-480 mg/L, and decreased sharply with increasing adsorbent concentration ranging from 1.0 to 5.0 g/L. An increase in sodium chloride (as supporting electrolyte) concentration was found to induce a negative effect while an increase in temperature was found to give rise to a positive effect on the chromium (VI) adsorption process. Compared to the various other adsorbents reported in the literature, the walnut hull in this study shows very good promise for practical applicability.

Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

NASA Astrophysics Data System (ADS)

Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

2016-05-01

A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g-1 and 96 mAh g-1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0-4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries.

Anion receptor compounds for non-aqueous electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

2000-09-19

A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

A Novel Phase-Transformation Activation Process toward Ni-Mn-O Nanoprism Arrays for 2.4 V Ultrahigh-Voltage Aqueous Supercapacitors.

PubMed

Zuo, Wenhua; Xie, Chaoyue; Xu, Pan; Li, Yuanyuan; Liu, Jinping

2017-09-01

One of the key challenges of aqueous supercapacitors is the relatively low voltage (0.8-2.0 V), which significantly limits the energy density and feasibility of practical applications of the device. Herein, this study reports a novel Ni-Mn-O solid-solution cathode to widen the supercapacitor device voltage, which can potentially suppress the oxygen evolution reaction and thus be operated stably within a quite wide potential window of 0-1.4 V (vs saturated calomel electrode) after a simple but unique phase-transformation electrochemical activation. The solid-solution structure is designed with an ordered array architecture and in situ nanocarbon modification to promote the charge/mass transfer kinetics. By paring with commercial activated carbon anode, an ultrahigh voltage asymmetric supercapacitor in neutral aqueous LiCl electrolyte is assembled (2.4 V; among the highest for single-cell supercapacitors). Moreover, by using a polyvinyl alcohol (PVA)-LiCl electrolyte, a 2.4 V hydrogel supercapacitor is further developed with an excellent Coulombic efficiency, good rate capability, and remarkable cycle life (>5000 cycles; 95.5% capacity retention). Only one cell can power the light-emitting diode indicator brightly. The resulting maximum volumetric energy density is 4.72 mWh cm -3 , which is much superior to previous thin-film manganese-oxide-based supercapacitors and even battery-supercapacitor hybrid devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolytic Transformation of Hexyhydro-1,3,5-Trinitro-1,3,5-Triazine (RDX) and 2,4,6-Trinitrotoluene (TNT) in Aqueous Solutions

DTIC Science & Technology

2005-08-01

several years (Bunce et al. 1997; de Lima Leite et al. 2003; Panizza and Cerisola 2004). Treatment is achieved by either oxidation (anodic) or reduction...Hexahydro-1,3,5-trinitro- 1,3,5-triazine mineralization by zerovalent iron and mixed anaerobic cultures,” Environ. Sci. Technol. 35, 4341-4346. Panizza

Electrolytic Transformation of Hexahydro-1,3,5-Trinitro-1,3,5-Triazine (RDX) and 2,4,6-Trintrotoluene (TNT) in Aqueous Solutions

DTIC Science & Technology

2005-08-01

several years (Bunce et al. 1997; de Lima Leite et al. 2003; Panizza and Cerisola 2004). Treatment is achieved by either oxidation (anodic) or reduction...Hexahydro-1,3,5-trinitro- 1,3,5-triazine mineralization by zerovalent iron and mixed anaerobic cultures,” Environ. Sci. Technol. 35, 4341-4346. Panizza

On the constituents of aqueous polyselenide electrolytes: A combined theoretical and Raman spectroscopic study

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

Goldbach, A.; Johnson, J.; Meisel, D.

1999-05-12

The speciation of aqueous polyselenide solutions at high pH values has been investigated by Raman and Uv/vis absorption spectroscopy. Complementary, ab initio molecular orbital calculations at the HF/6-31+G{sup *} level of theory have been carried out on the vibrational frequencies of polyselenide dianions Se{sub x}{sup 2{minus}} (x = 2--4), polyselenide radical anions Se{sub x}{sup {minus}} (x = 2, 3), and protonated polyselenides HSe{sub x}{sup {minus}} (x = 1--3) in order to substantiate the assignment of the experimental Raman spectra. Although the optical spectra suggest the successive formation of Se{sub 2}{sup 2{minus}}, Se{sub 3}{sup 2{minus}}, and Se{sub 4}{sup 2{minus}} with progressivemore » oxidation of the solutions, only two characteristic Raman bands are observed at 269 and 324 cm{sup {minus}1}. A sequence of overtones of the 269 cm{sup {minus}1} band is observed after excitation with blue light. Likewise strong overtones of the 324 cm{sup {minus}1} band appear after excitation with green light. The 269 cm{sup {minus}1} features is assigned to Se{sub 4}{sup 2{minus}} while the 324 cm{sup {minus}1} band is attributed to the radical anion Se{sub 2}{sup {minus}}. The occurrence of polyselenide radicals in aqueous solution is without precedent, and the formation of Se{sub 2}{sup {minus}} is ascribed to a photolytic process in the electrolyte. The only protonated species observed in this study is HSe{sup {minus}}, which is characterized by a Raman band at 2,303 cm{sup {minus}1}.« less

Manganese dioxide decoration of macroscopic carbon nanotube fibers: From high-performance liquid-based to all-solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Pendashteh, Afshin; Senokos, Evgeny; Palma, Jesus; Anderson, Marc; Vilatela, Juan J.; Marcilla, Rebeca

2017-12-01

Supercapacitors capable of providing high voltage, energy and power density but yet light, low volume occupying, flexible and mechanically robust are highly interesting and demanded for portable applications. Herein, freestanding flexible hybrid electrodes based on MnO2 nanoparticles grown on macroscopic carbon nanotube fibers (CNTf-MnO2) were fabricated, without the need of any metallic current collector. The CNTf, a support with excellent electrical conductivity, mechanical stability, and appropriate pore structure, was homogeneously decorated with porous akhtenskite ɛ-MnO2 nanoparticles produced via electrodeposition in an optimized organic-aqueous mixture. Electrochemical properties of these decorated fibers were evaluated in different electrolytes including a neutral aqueous solution and a pure 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid (PYR14TFSI). This comparison helps discriminate the various contributions to the total capacitance: (surface) Faradaic and non-Faradaic processes, improved wetting by aqueous electrolytes. Accordingly, symmetric supercapacitors with PYR14TFSI led to a high specific energy of 36 Wh· kgMnO2-1 (16 Wh·kg-1 including the weight of CNTf) and real specific power of 17 kW· kgMnO2-1 (7.5 kW kg-1) at 3.0 V with excellent cycling stability. Moreover, flexible all solid-state supercapacitors were fabricated using PYR14TFSI-based polymer electrolyte, exhibiting maximum energy density of 21 Wh·kg-1 and maximum power density of 8 kW kg-1 normalized by total active material.

Ti-substituted tunnel-type Na 0.44MnO 2 oxide as a negative electrode for aqueous sodium-ion batteries

DOE PAGES

Wang, Yuesheng; Liu, Jue; Lee, Byungju; ...

2015-03-25

The aqueous sodium-ion battery system is a safe and low-cost solution for large-scale energy storage, due to the abundance of sodium and inexpensive aqueous electrolytes. Although several positive electrode materials, e.g., Na 0.44MnO 2, were proposed, few negative electrode materials, e.g., activated carbon and NaTi 2(PO 4) 3, are available. Here we show that Ti-substituted Na 0.44MnO 2 (Na 0.44[Mn 1-xTi x]O 2) with tunnel structure can be used as a negative electrode material for aqueous sodium-ion batteries. This material exhibits superior cyclability even without the special treatment of oxygen removal from the aqueous solution. Atomic-scale characterizations based on sphericalmore » aberration-corrected electron microscopy and ab initio calculations are utilized to accurately identify the Ti substitution sites and sodium storage mechanism. Ti substitution tunes the charge ordering property and reaction pathway, significantly smoothing the discharge/charge profiles and lowering the storage voltage. Both the fundamental understanding and practical demonstrations suggest that Na 0.44[Mn 1-xTi x]O 2 is a promising negative electrode material for aqueous sodium-ion batteries.« less

Hierarchical micro- and mesoporous carbide-derived carbon as a high-performance electrode material in supercapacitors.

PubMed

Rose, Marcus; Korenblit, Yair; Kockrick, Emanuel; Borchardt, Lars; Oschatz, Martin; Kaskel, Stefan; Yushin, Gleb

2011-04-18

Ordered mesoporous carbide-derived carbon (OM-CDC) materials produced by nanocasting of ordered mesoporous silica templates are characterized by a bimodal pore size distribution with a high ratio of micropores. The micropores result in outstanding adsorption capacities and the well-defined mesopores facilitate enhanced kinetics in adsorption processes. Here, for the first time, a systematic study is presented, in which the effects of synthesis temperature on the electrochemical performance of these materials in supercapacitors based on a 1 M aqueous solution of sulfuric acid and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid are reported. Cyclic voltammetry shows the specific capacitance of the OM-CDC materials exceeds 200 F g(-1) in the aqueous electrolyte and 185 F g(-1) in the ionic liquid, when measured in a symmetric configuration in voltage ranges of up to 0.6 and 2 V, respectively. The ordered mesoporous channels in the produced OM-CDC materials serve as ion-highways and allow for very fast ionic transport into the bulk of the OM-CDC particles. At room temperature the enhanced ion transport leads to 75% and 90% of the capacitance retention at current densities in excess of ∼10 A g(-1) in ionic liquid and aqueous electrolytes, respectively. The supercapacitors based on 250-300 μm OM-CDC electrodes demonstrate an operating frequency of up to 7 Hz in aqueous electrolyte. The combination of high specific capacitance and outstanding rate capabilities of the OM-CDC materials is unmatched by state-of-the art activated carbons and strictly microporous CDC materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode

PubMed Central

2017-01-01

Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g–1. This is on par with the best solution-phase amine chemical capture technologies available today. PMID:28378994

Immobilized nickel hexacyanoferrate on activated carbons for efficient attenuation of radio toxic Cs(I) from aqueous solutions

NASA Astrophysics Data System (ADS)

Lalhmunsiama; Lalhriatpuia, C.; Tiwari, Diwakar; Lee, Seung-Mok

2014-12-01

The aim of this study is to immobilize nickel hexacyanoferrate onto the large surface of activated carbons (ACs) precursor to rice hulls and areca nut waste materials. These nickel hexacyanoferrate immobilized materials are then assessed in the effective attenuation of radio logically important cesium ions from aqueous solutions. The solid samples are characterized by the XRD analytical method and surface morphology is obtained from the SEM images. The batch reactor experiments show that an increase in sorptive pH (2.0-10.0) apparently not affecting the high percent uptake of Cs(I). Equilibrium modeling studies suggest that the data are reasonably and relatively fitted well to the Langmuir adsorption isotherm. Kinetic studies show that sorption process is fairly rapid and the kinetic data are fitted well to the pseudo-second order rate model. Increasing the background electrolyte concentration from 0.001 to 0.1 mol/L NaCl causes insignificant decrease in Cs(I) removal which infers the higher selectivity of these materials for Cs(I) from aqueous solutions. Further, the column reactor operations enable to obtain the breakthrough data which are then fitted to the Thomas non-linear equation as to obtain the loading capacity of column for Cs(I). The results show that the modified materials show potential applicability in the attenuation of radio toxic cesium from aqueous solution.

Titanium surface modification by microarc oxidation in electrolyte based on wollastonite and hydroxyapatite

NASA Astrophysics Data System (ADS)

Sharkeev, Yu. P.; Sedelnikova, M. B.; Komarova, E. G.; Khlusov, I. A.

2015-11-01

An investigation of titanium surface modification by microarc oxidation in the electrolyte based on wollastonite and hydroxyapatite was presented. The dependences of the coating properties on the microarc oxidation parameters were found. A variation of the process parameters allowed producing wollastonite-calcium phosphate coatings with aplate-like structure, thickness 25-30 µm, roughness 2.5-5.0 µm, and adhesion strength 57 MPa. The optimum microarc oxidation parameters such as the electrical voltage of 150 V, process duration of 5-10 min, and pulse duration of 100-300 µs were revealed. The wollastonite addition to the electrolyte based on the aqueous solution of phosphoric acid and hydroxyapatite allowed us to form wollastonite-calcium phosphate coatings on the titanium surface by the microarc oxidation method with enhanced strength properties and an increased ability to osseointegration.

Characterization of Sweetmeat Waste and Its Suitability for Sorption of As(III) in Aqueous Media.

PubMed

Islam, Md Mirajul; Adak, Asok; Paul, Prabir K

2017-04-01

  Presence of arsenic in effluents from mining, mineral processing, and metal plating industries pose a serious health hazard to human beings. In this research, suitability of cheap sweetmeat waste (SMW), which is sweet industry byproduct, was investigated for the treatment of As(III). The physicochemical properties of the sorbent were characterized. The SEM images revealed highly heterogeneous sorbent surface. XRD analysis showed the presence of different polysaccharides mainly containing hydroxyl functional group. FTIR analysis was also performed to confirm the functional groups present in the sorbent. Batch experiments were conducted for kinetic analysis, effect of initial As(III) concentration, sorbent dose, electrolytes, pH, and temperature in order to understand sorption behavior. Presence of electrolyte, solution pH, and temperature were found to affect the performance of the sorbent. The sorption followed pseudo-second order reaction and Langmuir isotherm model best. The studies revealed SMW to be an efficient media for removal of As(III) from aqueous environment.

Ewald Summation Approach to Potential Models of Aqueous Electrolytes Involving Gaussian Charges and Induced Dipoles: Formal and Simulation Results

DOE PAGES

Chialvo, Ariel A.; Vlcek, Lukas

2014-11-01

We present a detailed derivation of the complete set of expressions required for the implementation of an Ewald summation approach to handle the long-range electrostatic interactions of polar and ionic model systems involving Gaussian charges and induced dipole moments with a particular application to the isobaricisothermal molecular dynamics simulation of our Gaussian Charge Polarizable (GCP) water model and its extension to aqueous electrolytes solutions. The set comprises the individual components of the potential energy, electrostatic potential, electrostatic field and gradient, the electrostatic force and the corresponding virial. Moreover, we show how the derived expressions converge to known point-based electrostatic counterpartsmore » when the parameters, defining the Gaussian charge and induced-dipole distributions, are extrapolated to their limiting point values. Finally, we illustrate the Ewald implementation against the current reaction field approach by isothermal-isobaric molecular dynamics of ambient GCP water for which we compared the outcomes of the thermodynamic, microstructural, and polarization behavior.« less

Finite-size effects in simulations of electrolyte solutions under periodic boundary conditions

NASA Astrophysics Data System (ADS)

Thompson, Jeffrey; Sanchez, Isaac

The equilibrium properties of charged systems with periodic boundary conditions may exhibit pronounced system-size dependence due to the long range of the Coulomb force. As shown by others, the leading-order finite-size correction to the Coulomb energy of a charged fluid confined to a periodic box of volume V may be derived from sum rules satisfied by the charge-charge correlations in the thermodynamic limit V -> ∞ . In classical systems, the relevant sum rule is the Stillinger-Lovett second-moment (or perfect screening) condition. This constraint implies that for large V, periodicity induces a negative bias of -kB T(2 V) - 1 in the total Coulomb energy density of a homogeneous classical charged fluid of given density and temperature. We present a careful study of the impact of such finite-size effects on the calculation of solute chemical potentials from explicit-solvent molecular simulations of aqueous electrolyte solutions. National Science Foundation Graduate Research Fellowship Program, Grant No. DGE-1610403.

Organic Solar Cells Based on Electrodeposited Polyaniline Films

NASA Astrophysics Data System (ADS)

Inoue, Kei; Akiyama, Tsuyoshi; Suzuki, Atsushi; Oku, Takeo

2012-04-01

Polyaniline thin films as hole transporting layers were fabricated on transparent indium-tin-oxide electrodes by electrodeposition of aniline in an aqueous H2SO4 electrolyte solution. Emerald-green polyaniline films were obtained, which showed stable redox waves. A mixed solution of polythiophene and fullerene derivative was spin-coated onto the electrodeposited polyaniline film. After the modification of titanium oxide film on the surface of the polythiophene/fullerene layer, an aluminum electrode was fabricated by vacuum deposition. The obtained solar cells generated stable photocurrent and photovoltage under light illumination.

Structure, hydrolysis, and diffusion of aqueous vanadium ions from Car-Parrinello molecular dynamics

NASA Astrophysics Data System (ADS)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2016-09-01

A molecular level understanding of the properties of electroactive vanadium species in aqueous solution is crucial for enhancing the performance of vanadium redox flow batteries. Here, we employ Car-Parrinello molecular dynamics simulations based on density functional theory to investigate the hydration structures, first hydrolysis reaction, and diffusion of aqueous V2+, V3+, VO2+, and VO 2+ ions at 300 K. The results indicate that the first hydration shell of both V2+ and V3+ contains six water molecules, while VO2+ is coordinated to five and VO 2+ to three water ligands. The first acidity constants (pKa) estimated using metadynamics simulations are 2.47, 3.06, and 5.38 for aqueous V3+, VO 2+ , and VO2+, respectively, while V2+ is predicted to be a fairly weak acid in aqueous solution with a pKa value of 6.22. We also show that the presence of chloride ions in the first coordination sphere of the aqueous VO 2+ ion has a significant impact on water hydrolysis leading to a much higher pKa value of 4.8. This should result in a lower propensity of aqueous VO 2+ for oxide precipitation reaction in agreement with experimental observations for chloride-based electrolyte solutions. The computed diffusion coefficients of vanadium species in water at room temperature are found to increase as V 3 + < VO 2 + < V O 2 + < V 2 + and thus correlate with the simulated hydrolysis constants, namely, the higher the pKa value, the greater the diffusion coefficient.

Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

PubMed Central

Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

2016-01-01

A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g−1 and 96 mAh g−1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0–4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries. PMID:27174224

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.

Molecular Simulations of Graphene-Based Electric Double-Layer Capacitors

NASA Astrophysics Data System (ADS)

Kalluri, Raja K.; Konatham, Deepthi; Striolo, Alberto

2011-03-01

Towards deploying renewable energy sources it is crucial to develop efficient and cost-effective technologies to store electricity. Traditional batteries are plagued by a number of practical problems that at present limit their widespread applicability. One possible solution is represented by electric double-layer capacitors (EDLCs). To deploy EDLCs at the large scale it is necessary to better understand how electrolytes pack and diffuse within narrow charged pores. We present here simulation results for the concentrated aqueous solutions of NaCl, CsCl, and NaI confined within charged graphene-based porous materials. We discuss how the structure of confined water, the salt concentration, the ions size, and the surface charge density determine the accumulation of electrolytes within the porous network. Our results, compared to data available for bulk systems, are critical for relating macroscopic observations to molecular-level properties of the confined working fluids. Research supported by the Department of Energy.

Combined soft and hard X-ray ambient pressure photoelectron spectroscopy studies of semiconductor/electrolyte interfaces

DOE PAGES

Starr, David E.; Favaro, Marco; Abdi, Fatwa F.; ...

2017-05-18

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly a ddress. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hardmore » X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. Finally, the article concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO 4/aqueous potassium phosphate electrolyte interface.« less

Hybrid capacitors utilizing halogen-based redox reactions at interface between carbon positive electrode and aqueous electrolytes

NASA Astrophysics Data System (ADS)

Yamazaki, Shigeaki; Ito, Tatsuya; Murakumo, Yuka; Naitou, Masashi; Shimooka, Toshiharu; Yamagata, Masaki; Ishikawa, Masashi

2016-09-01

We propose novel hybrid capacitors (HCs) with electrolyte-involved redox reactions of bromide or iodide species by pretreatment of an activated carbon positive electrode. The treatment is simple; impregnation of pores at an activated carbon fiber cloth (ACFC) as a positive electrode with bromine- or iodine-containing water before cell assembly. The treated positive electrode is applied to a HC cell with a non-treated negative electrode of ACFC and its electrochemical performance is investigated by galvanostatic cycling and leakage current tests. Few studies on such "electrolytic" charge storage systems have provided acceptable capacitor performance because of inevitable self-discharge caused by diffusion of charged species form an electrode to the other one through an electrolyte. Nevertheless, our electrolyte-redox-based HCs show excellent performance without undesirable diffusion of charged species. Moreover, the present HC utilizing a bromide redox system fulfills a practical cell voltage of 1.8 V in spite of an aqueous electrolyte system. This high voltage provides excellent energy density, which is 5 times higher than that in a conventional aqueous electric double-layer capacitor (EDLC), and 1.2 times higher even than that in a 2.7 V-class non-aqueous EDLC, while keeping high charge-discharge rate capability.

The influence of current collector corrosion on the performance of electrochemical capacitors

NASA Astrophysics Data System (ADS)

Wojciechowski, Jarosław; Kolanowski, Łukasz; Bund, Andreas; Lota, Grzegorz

2017-11-01

This paper discusses the effect of current collector (stainless steel 316L) corrosion on the performance of electrochemical capacitors operated in aqueous electrolytes. This topic seems to be often neglected in scientific research. The studied electrolytes were 1 M H2SO4, 1 M KI, 1 M Na2SO4, 1 M KOH and 6 M KOH. The corrosion process was investigated by means of selected direct and alternating current techniques. The surface of the current collectors as well as the corrosion products were characterised using scanning electron microscopy, energy-dispersive X-ray spectroscopy, Raman spectroscopy and atomic force microscopy. Stainless steel 316L in alkaline solutions is characterised by the lowest values of corrosion potentials whereas the potentials in acidic media become the most noble. Our studies show that corrosion potentials increase with decreasing pH value. This phenomenon can be explained with the formation of passive oxide films on the stainless steel current collectors. The passive oxide films are usually thicker and more porous in alkaline solutions than that in the other electrolytes. The processes occurring at the electrode/electrolyte interfaces strongly influence the working parameters of electrochemical capacitors such as voltage, working potentials of single electrodes, self-discharge as well as the internal resistance and cycling stability.

Influence of sealing post-treatments on the corrosion resistance of PEO coated AZ91 magnesium alloy

NASA Astrophysics Data System (ADS)

Mingo, B.; Arrabal, R.; Mohedano, M.; Llamazares, Y.; Matykina, E.; Yerokhin, A.; Pardo, A.

2018-03-01

The effect of three different post-treatments carried out on Plasma Electrolytic Oxidation (PEO) coated magnesium alloys are evaluated in terms of characterisation and corrosion resistance. Special interest is given to the role of a common additive (NaF) to the coating properties. The post-treatments are based on immersion sealing processes in aqueous solutions of inorganic salts (cerium and stannate based salts) and alcoholic solution of an organic acid (octodecylphosphate acid, ODP). Sealing mechanisms for each post-treatment are proposed. Cerium and stannate sealings are based on filling of the pores with the products of dissolution/precipitation reactions, while the ODP acid sealing is based on the formation of a thin layer of ODP over the coating through specific interactions between the polar part of the organic acid and the coating surface. All coatings are evaluated by salt fog test and analysed by electrochemical impedance spectroscopy. All sealings show a slight increase in the corrosion resistance of the coatings formed in the NaF-free electrolyte, but their positive influence is boosted in case of the coatings obtained in the NaF-containing electrolyte. This is related to the chemical and morphological changes at the coating surface induced by the presence of NaF in the electrolyte.

Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

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

Small, Leo J.; Pratt, Harry; Staiger, Chad

We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

Bio-Fluid Transport Models Through Nano and Micro-Fluidic Components

DTIC Science & Technology

2005-08-01

nm of the wall in steady electroosmotic flow with good accuracy. The nPIV data were in excellent agreement with the model predictions for monovalent...first experimental probe inside the electric double layer in electroosmotic flow of an aqueous electrolyte solution. 15. NUMBER OF PAGES 225 14...SUBJECT TERMS Micro And Nanofluidics, Electroosmotic Flow, Nano Particle Image Velocimetry 16. PRICE CODE 17. SECURITY CLASSIFICATION OF REPORT

Membrane reference electrode

DOEpatents

Redey, L.; Bloom, I.D.

1988-01-21

A reference electrode utilizes a small thin, flat membrane of a highly conductive glass placed on a small diameter insulator tube having a reference material inside in contact with an internal voltage lead. When the sensor is placed in a non-aqueous ionic electrolytic solution, the concentration difference across the glass membrane generates a low voltage signal in precise relationship to the concentration of the species to be measured, with high spatial resolution. 2 figs.

Prediction of Crack Growth Aqueous Environments.

DTIC Science & Technology

1983-06-01

one- dimensional one. The mathematical model for the electrical representation shown in Figure 1 requires solutions to a set of differential equations ... equation (5) is equivalent to that at a plane-parallel electrode. That is, it contains the info~rmation that would be available if it were possible to...concentration, and A" expresses the electrode electrolyte area per unit length that is actively engaged in reaction. The other parameters in equation (7

Proton adsorption onto alumina: extension of multisite complexation (MUSIC) theory

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

Nagashima, K.; Blum, F.D.

1999-09-01

The adsorption isotherm of protons onto a commercial {gamma}-alumina sample was determined in aqueous nitric acid with sodium nitrate as a background electrolyte. Three discrete regions could be discerned in the log-log plots of the proton isotherm determined at the solution pH 5 to 2. The multisite complexation (MUSIC) model was modified to analyze the simultaneous adsorption of protons onto various kinds of surface species.

Density functional study on the structural and thermodynamic properties of aqueous DNA-electrolyte solution in the framework of cell model.

PubMed

Wang, Ke; Yu, Yang-Xin; Gao, Guang-Hua

2008-05-14

A density functional theory (DFT) in the framework of cell model is proposed to calculate the structural and thermodynamic properties of aqueous DNA-electrolyte solution with finite DNA concentrations. The hard-sphere contribution to the excess Helmholtz energy functional is derived from the modified fundamental measure theory, and the electrostatic interaction is evaluated through a quadratic functional Taylor expansion around a uniform fluid. The electroneutrality in the cell leads to a variational equation with a constraint. Since the reference fluid is selected to be a bulk phase, the Lagrange multiplier proves to be the potential drop across the cell boundary (Donnan potential). The ion profiles and electrostatic potential profiles in the cell are calculated from the present DFT-cell model. Our DFT-cell model gives better prediction of ion profiles than the Poisson-Boltzmann (PB)- or modified PB-cell models when compared to the molecular simulation data. The effects of polyelectrolyte concentration, ion size, and added-salt concentration on the electrostatic potential difference between the DNA surface and the cell boundary are investigated. The expression of osmotic coefficient is derived from the general formula of grand potential. The osmotic coefficients predicted by the DFT are lower than the PB results and are closer to the simulation results and experimental data.

Microgravity effects on electrodeposition of metals and metal-cermet mixtures

NASA Technical Reports Server (NTRS)

Maybee, George W.; Riley, Clyde; Coble, H. Dwain

1987-01-01

An experimental system, designed to investigate the potential advantages of electrodeposition in microgravity, is being developed by the McDonnell Douglas Astronautics Company-Huntsville Division and the University of Alabama in Huntsville. It is intended to fly as an Orbiter payload when NASA resumes STS operations. The system will provide power, thermal conditioning, command and control for the production of electrodeposits; system performance data will be recorded for post-flight analysis. Plated metal surfaces will be created using simple electrolytic cells with pure metal electrodes immersed in aqueous electrolytic solutions. Crystalline structure and other properties will be analyzed to identify differences between samples produced in flight and those obtained from ground-based operations.

The impact of electrolyte on the adsorption of the anionic surfactant methyl ester sulfonate at the air-solution interface: Surface multilayer formation.

PubMed

Xu, H; Thomas, R K; Penfold, J; Li, P X; Ma, K; Welbourne, R J L; Roberts, D W; Petkov, J T

2018-02-15

The methyl ester sulfonates represent a promising group of anionic surfactants which have the potential for improved performance and biocompatibility in a range of applications. Their solution properties, in particular their tolerance to hard water, suggests that surface ordering may occur in the presence of multi-valent counterion. Understanding their adsorption properties in a range of different circumstances is key to the exploitation of their potential. Neutron reflectivity and surface tension have been used to characterise the adsorption at the air-aqueous solution interface of the anionic surfactant sodium tetradecanoic 2-sulfo 1-methyl ester, C 14 MES, in the absence of electrolyte and in the presence of mono, di, and tri-valent counterions, Na + , Ca 2+ , and Al 3+ . In particular the emphasis has been on exploring the tendency to form layered structures at the interface. In the absence of electrolyte and in the presence of NaCl and CaCl 2 and AlCl 3 at low concentrations monolayer adsorption is observed, and the addition of electrolyte results in enhanced adsorption. In the presence of NaCl and CaCl 2 only monolayer adsorption is observed. However at higher AlCl 3 concentrations surface multilayer formation is observed, in which the number of bilayers at the surface depends upon the surfactant and AlCl 3 concentrations. Copyright © 2017 Elsevier Inc. All rights reserved.

Pitting corrosion of titanium. The relationship between pitting potential and competitive anion adsorption at the oxide film/electrolyte interface

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

Basame, S.B.; White, H.S.

2000-04-01

The potential-dependent breakdown of the native oxide film ({approximately}20 {angstrom} thick) on titanium has been investigated in aqueous Br{sup {minus}} solutions and in solutions that contain a mixture of Br{sup {minus}} and anions that inhibit oxide breakdown (i.e., Cl{sup {minus}}, I{sup {minus}}, SO{sub 4}{sup 2{minus}}, Fe(CN){sub 6}{sup 4{minus}}, and Fe(CN){sub 6}{sup 3{minus}}). The oxide film is unstable in neutral pH solutions containing only Br{sup {minus}}, resulting in the formation of stable corrosion pits at relatively low potentials ({approximately}1.4 V vs. Ag/AgCl). The pitting potential, E{sub p}, is strongly dependent upon the concentration of Br{sup {minus}}, and can be modeled usingmore » a Langmuir isotherm to describe the adsorption of Br{sup {minus}} at the oxide film/electrolyte interface. Addition of a second anion inhibits oxide film breakdown, as indicated by a large positive shift in E{sub p} and a decrease in the number of stable corrosion pits. The dependence of E{sub p} on the relative concentrations of Br{sup {minus}} and the inhibitor anion is consistent with competitive adsorption of the anions. Equilibrium adsorption coefficients for I{sup {minus}}, Br{sup {minus}}, and Cl{sup {minus}} are estimated from the dependence of E{sub p} on anion concentration. The results are used to establish a physical basis for the anomalously low pitting potential for titanium in aqueous Br{sup {minus}} solutions.« less

Chemical etching of stainless steel 301 for improving performance of electrochemical capacitors in aqueous electrolyte

NASA Astrophysics Data System (ADS)

Jeżowski, P.; Nowicki, M.; Grzeszkowiak, M.; Czajka, R.; Béguin, F.

2015-04-01

The main purpose of the study was to increase the surface roughness of stainless steel 301 current collectors by etching, in order to improve the electrochemical performance of electrical double-layer capacitors (EDLC) in 1 mol L-1 lithium sulphate electrolyte. Etching was realized in 1:3:30 (HNO3:HCl:H2O) solution with times varying up to 10 min. For the considered 15 μm thick foil and a mass loss around 0.4 wt.%, pitting was uniform, with diameter of pits ranging from 100 to 300 nm. Atomic force microscopy (AFM) showed an increase of average surface roughness (Ra) from 5 nm for the as-received stainless steel foil to 24 nm for the pitted material. Electrochemical impedance spectroscopy realized on EDLCs with coated electrodes either on as-received or pitted foil in 1 mol L-1 Li2SO4 gave equivalent distributed resistance (EDR) of 8 Ω and 2 Ω, respectively, demonstrating a substantial improvement of collector/electrode interface after pitting. Correlatively, the EDLCs with pitted collector displayed a better charge propagation and low ohmic losses even at relatively high current of 20 A g-1. Hence, chemical pitting of stainless steel current collectors is an appropriate method for optimising the performance of EDLCs in neutral aqueous electrolyte.

Catching TFSI: A Computational-Experimental Approach to β-Cyclodextrin-Based Host-Guest Systems as electrolytes for Li-Ion Batteries.

PubMed

Jeschke, Steffen; Jankowski, Piotr; Best, Adam S; Johansson, Patrik

2018-03-12

Cyclodextrins (CDs) are pyranoside-based macromolecules with a hydrophobic cavity to encapsulate small molecules. They are used as molecular vehicles, for instance in pharmaceutical drug delivery or as solubility enhancer of monomers for their polymerization in aqueous solution. In this context, it was discovered about 10 years ago that the bis(trifluoromethylsulonyl)imide (TFSI) anion forms host-guest complexes with βCD in aqueous media. This sparked interest in using the TFSI anion in lithium-based battery electrolytes open for its encapsulation by βCD as an attractive approach to increase the contribution of the cation to the total ion conductivity. By using semi-empirical quantum mechanical (SQM) methods and the conductor-like screening model for a real solvent (COSMO-RS), a randomly methylated βCD (RMβCD) is here identified as a suitable host for TFSI when using organic solvents often used in battery technology. By combining molecular dynamics (MD) simulations with different NMR and FTIR experiments, the formation of the corresponding RMβCD-TFSI complex was investigated. Finally, the effects of the addition RMβCD to a set of electrolytes on the ion conductivity are measured and explained using three distinct scenarios. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of Surface Potential and Electrical Double-Layer Structure at the Aqueous Electrolyte-Nanoparticle Interface

NASA Astrophysics Data System (ADS)

Brown, Matthew A.; Abbas, Zareen; Kleibert, Armin; Green, Richard G.; Goel, Alok; May, Sylvio; Squires, Todd M.

2016-01-01

The structure of the electrical double layer has been debated for well over a century, since it mediates colloidal interactions, regulates surface structure, controls reactivity, sets capacitance, and represents the central element of electrochemical supercapacitors. The surface potential of such surfaces generally exceeds the electrokinetic potential, often substantially. Traditionally, a Stern layer of nonspecifically adsorbed ions has been invoked to rationalize the difference between these two potentials; however, the inability to directly measure the surface potential of dispersed systems has rendered quantitative measurements of the Stern layer potential, and other quantities associated with the outer Helmholtz plane, impossible. Here, we use x-ray photoelectron spectroscopy from a liquid microjet to measure the absolute surface potentials of silica nanoparticles dispersed in aqueous electrolytes. We quantitatively determine the impact of specific cations (Li+ , Na+ , K+ , and Cs+ ) in chloride electrolytes on the surface potential, the location of the shear plane, and the capacitance of the Stern layer. We find that the magnitude of the surface potential increases linearly with the hydrated-cation radius. Interpreting our data using the simplest assumptions and most straightforward understanding of Gouy-Chapman-Stern theory reveals a Stern layer whose thickness corresponds to a single layer of water molecules hydrating the silica surface, plus the radius of the hydrated cation. These results subject electrical double-layer theories to direct and falsifiable tests to reveal a physically intuitive and quantitatively verified picture of the Stern layer that is consistent across multiple electrolytes and solution conditions.

Enzyme-modified electrolyte-gated organic field-effect transistors

NASA Astrophysics Data System (ADS)

Buth, Felix; Donner, Andreas; Stutzmann, Martin; Garrido, Jose A.

2012-10-01

Organic solution-gated field-effect transistors (SGFETs) can be operated at low voltages in aqueous environments, paving the way to the use of organic semiconductors in bio-sensing applications. However, it has been shown that these devices exhibit only a rather weak sensitivity to standard electrolyte parameters such as pH and ionic strength. In order to increase the sensitivity and to add specificity towards a given analyte, the covalent attachment of functional groups and enzymes to the device surface would be desirable. In this contribution we demonstrate that enzyme modified organic SGFETs can be used for the in-situ detection of penicillin in the low μM regime. In a first step, silane molecules with amine terminal groups are grafted to α-sexithiophene-based thin film transistors. Surface characterization techniques like X-ray photoemission confirm the modification of the surface with these functional groups, which are stable in standard aqueous electrolytes. We show that the presence of surface-bound amphoteric groups (e.g. amino or carboxylic moieties) increases the pH-sensitivity of the organic SGFETs. In addition, these groups serve as anchoring sites for the attachment of the enzyme penicillinase. The resulting enzyme-FETs are used for the detection of penicillin, enabling the study of the influence of the buffer strength and the pH of the electrolyte on the enzyme kinetics. The functionalization of the organic FETs shown here can be extended to a large variety of enzymes, allowing the specific detection of different chemical and biochemical analytes.

Electrolytic conductivity at 0.5 S m-1 and 5 mS m-1

NASA Astrophysics Data System (ADS)

Seitz, S.; Sander, B.; Snedden, A.; DeLeeBeeck, L.; Canaza, G. T.; Asakai, T.; Maksimov, I.; Song, X.; Wang, H.; Kozlowski, W.; Dumanska, J.; Jakusovszky, B.; Szilágyi, Z. N.; Gavrilkin, V.; Stennik, O.; Ovchinnikov, Y.; Gonzaga, F. B.; da Cruz Cunha, K.; Ferraz, S. F.; Hanková, Z.; Máriássy, M.; Vicarova, M.; Vospelova, A.; Ortiz-Aparicio, J. L.; Lara-Manzano, J. V.; Uribe-Godínez, J.; Stoica, D.; Fisicaro, P.; Suvorov, V. I.; Konopelko, L. A.; Smirnov, A. M.; Amaya, R. C.; Quezada, H. T.

2017-01-01

Key Comparison CCQM-K36.2016 was a follow-up comparison for K36 and provided updated support for the corresponding calibration and measurement capability (CMC) entries in the BIPM CMC database. It aimed to demonstrate the capabilities of the participating NMIs to measure electrolytic conductivity of aqueous electrolyte solutions in the conductivity range 0.15 S m-1 to 1.5 S m-1 and in the conductivity range 1.5 mS m-1 to 15 mS m-1. To this end electrolytic conductivity of a potassium chloride solution (nominal conductivity 0.5 S m-1) and of a HCl solution (nominal conductivity 5 mS m-1) had to be measured. 17 NMIs participated in the comparison. The key comparison reference value (KCRV) of the KCl solution was (0.50999 +/-0.00032) S m-1 and the KCRV of the HCl solution was (4.9877 +/-0.012) mS m-1. Both values were estimated from the medians of the results considered eligible for KCRV calculation. They were given with their expanded uncertainties (95% coverage). The majority of the 0.5 S m-1 results were consistent with the KCRV. Two institutes showed a small inconsistency, one outlier was observed. The conductivity of the HCl solution showed a small, but steady linear drift of 0.00006843 mS m-1 per day during the measurement period and was corrected for KCRV calculation. Some institutes reported unstable measurement conditions for this solution. The results of seven participants have been inconsistent with the KCRV. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Rational Development of Neutral Aqueous Electrolytes for Zinc–Air Batteries

PubMed Central

Clark, Simon; Latz, Arnulf

2017-01-01

Abstract Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc–air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders‐of‐magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell‐level performance of pH‐buffered aqueous electrolytes. We apply our model to conduct the first continuum‐scale simulation of secondary ZABs using aqueous ZnCl2–NH4Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine‐containing solids may precipitate in addition to ZnO. PMID:28898553

Surface Charge Effects on the Electro-Orientation of Insulating Nanotubes in Aqueous Electrolytes

NASA Astrophysics Data System (ADS)

Cetindag, Semih; Tiwari, Bishnu; Zhang, Dongyan; Yap, Yoke Khin; Kim, Sangil; Shan, Jerry W.

2017-11-01

While the alignment of electrically conductive nanowires and nanotubes by electric fields in liquid solution has been well studied, much less is known about the electro-orientation of insulating 1D particles, such as boron-nitride nanotubes (BNNTs). Here, we demonstrate for the first time the electro-orientation of individual insulating BNNTs in aqueous KCl solutions under AC fields. Comparison to theory indicates that the observed frequency response is not related to the crossover for Maxwell-Wagner interfacial polarization. Instead, the cross-over frequency in the low-frequency regime scales as the square root of solution conductivity, indicating that alignment is associated with the formation and motion of an electrical double layer (EDL), much like induced-charge electro-osmosis for a conducting particle. However, the mechanism for the formation of the EDL is presumably different for insulating particles like BNNTs as compared to conductors. By varying the surface charge of the particle by changing pH, we show that the alignment rate increases with increasing surface charge, and is likely a result of counter-ion migration and EDL polarization under the influence of applied electric field. Thus, particle surface charge (large Dukhin number) is believed to play a vital role in the electro-orientation of insulating particles in aqueous solutions. NSF CBET-1604931 and NSF DMR-1261910.

Electrodeposition of Metals in Microgravity Conditions

NASA Technical Reports Server (NTRS)

Nishikawa, K.; Homma, T.; Chassaing, E.; Rosso, M.; Fukunaka, Y.

2012-01-01

Metal electrodeposition may introduce various morphological variations depending on the electrolytic conditions including cell configurations. For liquid electrolytes, a precise study of these deposits may be complicated by convective motion due to buoyancy. Zero-gravity (0-G) condition provided by drop shaft or parabolic flight gives a straightforward mean to avoid this effect: we present here 0-G electrodeposition experiments, which we compare to ground experiments (1-G). Two electrochemical systems were studied by laser interferometry, allowing to measure the concentration variations in the electrolyte: copper deposition from copper sulfate aqueous solution and lithium deposition from an ionic liquid containing LiTFSI. For copper, concentration variations were in good agreement with theory. For lithium, an apparent induction time was observed for the concentration evolution at 1-G: due to this induction time and to the low diffusion coefficient in ionic liquid, the concentration variations were hardly measurable in the parabolic flight 0-G periods of 20 seconds.

Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

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

Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita

To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of themore » Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.« less

Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions

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

Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.

Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less

Anions dramatically enhance proton transfer through aqueous interfaces

PubMed Central

Mishra, Himanshu; Enami, Shinichi; Nielsen, Robert J.; Hoffmann, Michael R.; Goddard, William A.; Colussi, Agustín J.

2012-01-01

Proton transfer (PT) through and across aqueous interfaces is a fundamental process in chemistry and biology. Notwithstanding its importance, it is not generally realized that interfacial PT is quite different from conventional PT in bulk water. Here we show that, in contrast with the behavior of strong nitric acid in aqueous solution, gas-phase HNO3 does not dissociate upon collision with the surface of water unless a few ions (> 1 per 106 H2O) are present. By applying online electrospray ionization mass spectrometry to monitor in situ the surface of aqueous jets exposed to HNO3(g) beams we found that production increases dramatically on > 30-μM inert electrolyte solutions. We also performed quantum mechanical calculations confirming that the sizable barrier hindering HNO3 dissociation on the surface of small water clusters is drastically lowered in the presence of anions. Anions electrostatically assist in drawing the proton away from lingering outside the cluster, whose incorporation is hampered by the energetic cost of opening a cavity therein. Present results provide both direct experimental evidence and mechanistic insights on the counterintuitive slowness of PT at water-hydrophobe boundaries and its remarkable sensitivity to electrostatic effects. PMID:22689964

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02691a Click here for additional data file.

PubMed Central

Mazzini, Virginia

2017-01-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity. PMID:29147533

Half-cell potentials of semiconductive simple binary sulphides in aqueous solution

USGS Publications Warehouse

Sato, M.

1966-01-01

Theoretical consideration of the charge-transfer mechanism operative in cells with an electrode of a semiconductive binary compound leads to the conclusion that the half-cell potential of such a compound is not only a function of ionic activities in the electrolytic solution, but also a function of the activities of the component elements in the compound phase. The most general form of the electrode equation derived for such a compound with a formula MiXj which dissociates into Mj+ and Xi- ions in aqueous solution is. EMiXj = EMiXj0 + R T 2 ij ln [ (sua Mj+)aqi ?? (suaX)jMiXj/ (suaXi-)aqj ?? (suaM)iMiXj],. where. EMiXj0 = 1 2(EM,Mj+0 + EXi-,X). The equation can be modified to other forms. When applied to semiconductive simple binary sulphides, these equations appear to give better descriptions of the observed electrode potentials of such sulphides than any other proposed equations. ?? 1966.

Ionic current rectification in organic solutions with quartz nanopipettes.

PubMed

Yin, Xiaohong; Zhang, Shudong; Dong, Yitong; Liu, Shujuan; Gu, Jing; Chen, Ye; Zhang, Xin; Zhang, Xianhao; Shao, Yuanhua

2015-09-01

The study of behaviors of ionic current rectification (ICR) in organic solutions with quartz nanopipettes is reported. ICR can be observed even in organic solutions using quartz pipettes with diameters varied from several to dozens of nanometers, and the direction of ICR is quite different from the ICR observed in aqueous phase. The influences of pore size, electrolyte concentration, and surface charge on the ICR have been investigated carefully. Water in organic solutions affects the direction and extent of ICR significantly. Mechanisms about the formation of an electrical double layer (EDL) on silica in organic solutions with different amount of water have been proposed. An improved method, which can be employed to detect trace water in organic solutions, has been implemented based on Au ultramicroelectrodes with cathodic differential pulse stripping voltammetry.

Optimization of Design Parameters and Operating Conditions of Electrochemical Capacitors for High Energy and Power Performance

NASA Astrophysics Data System (ADS)

Ike, Innocent S.; Sigalas, Iakovos; Iyuke, Sunny E.

2017-03-01

Theoretical expressions for performance parameters of different electrochemical capacitors (ECs) have been optimized by solving them using MATLAB scripts as well as via the MATLAB R2014a optimization toolbox. The performance of the different kinds of ECs under given conditions was compared using theoretical equations and simulations of various models based on the conditions of device components, using optimal values for the coefficient associated with the battery-kind material ( K BMopt) and the constant associated with the electrolyte material ( K Eopt), as well as our symmetric electric double-layer capacitor (EDLC) experimental data. Estimation of performance parameters was possible based on values for the mass ratio of electrodes, operating potential range ratio, and specific capacitance of electrolyte. The performance of asymmetric ECs with suitable electrode mass and operating potential range ratios using aqueous or organic electrolyte at appropriate operating potential range and specific capacitance was 2.2 and 5.56 times greater, respectively, than for the symmetric EDLC and asymmetric EC using the same aqueous electrolyte, respectively. This enhancement was accompanied by reduced cell mass and volume. Also, the storable and deliverable energies of the asymmetric EC with suitable electrode mass and operating potential range ratios using the proper organic electrolyte were 12.9 times greater than those of the symmetric EDLC using aqueous electrolyte, again with reduced cell mass and volume. The storable energy, energy density, and power density of the asymmetric EDLC with suitable electrode mass and operating potential range ratios using the proper organic electrolyte were 5.56 times higher than for a similar symmetric EDLC using aqueous electrolyte, with cell mass and volume reduced by a factor of 1.77. Also, the asymmetric EDLC with the same type of electrode and suitable electrode mass ratio, working potential range ratio, and proper organic electrolyte showed enhanced performance compared with the conventional symmetric EDLC using aqueous electrolyte, with reduced cell mass and volume. These results can obviously reduce the number of experiments required to determine the optimum manufacturing design for ECs and also demonstrate that use of an asymmetric electrode and organic electrolyte was very successful for improving the performance of the EC, with reduced cell mass and volume. These results can also act as guidelines for design, fabrication, and operation of electrochemical capacitors with outstanding storable energy, energy density, and power density.

Organic-Silica Interactions in Saline: Elucidating the Structural Influence of Calcium in Low-Salinity Enhanced Oil Recovery.

PubMed

Desmond, J L; Juhl, K; Hassenkam, T; Stipp, S L S; Walsh, T R; Rodger, P M

2017-09-08

Enhanced oil recovery using low-salinity solutions to sweep sandstone reservoirs is a widely-practiced strategy. The mechanisms governing this remain unresolved. Here, we elucidate the role of Ca 2+ by combining chemical force microscopy (CFM) and molecular dynamics (MD) simulations. We probe the influence of electrolyte composition and concentration on the adsorption of a representative molecule, positively-charged alkylammonium, at the aqueous electrolyte/silica interface, for four electrolytes: NaCl, KCl, MgCl 2 , and CaCl 2 . CFM reveals stronger adhesion on silica in CaCl 2 compared with the other electrolytes, and shows a concentration-dependent adhesion not observed for the other electrolytes. Using MD simulations, we model the electrolytes at a negatively-charged amorphous silica substrate and predict the adsorption of methylammonium. Our simulations reveal four classes of surface adsorption site, where the prevalence of these sites depends only on CaCl 2 concentration. The sites relevant to strong adhesion feature the O - silica site and Ca 2+ in the presence of associated Cl - , which gain prevalence at higher CaCl 2 concentration. Our simulations also predict the adhesion force profile to be distinct for CaCl 2 compared with the other electrolytes. Together, these analyses explain our experimental data. Our findings indicate in general how silica wettability may be manipulated by electrolyte concentration.

The origin of facet selectivity and alignment in anatase TiO 2 nanoparticles in electrolyte solutions: implications for oriented attachment in metal oxides

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

Sushko, M. L.; Rosso, K. M.

Atomic-to-mesoscale simulations were used to reveal the origin of oriented attachment between anatase TiO2 nanoparticles in aqueous HCl solutions. Analysis of the distance and pH dependence of interparticle interactions demonstrates that ion correlation forces are responsible for facet-specific attraction and rotation into lattice co-alignment at long-range. These forces give rise to a metastable solvent separated capture minimum on the disjoining pressure-distance curve, with the barrier to attachment largely due to steric hydration forces from structured intervening solvent.

Zeolite-based hemostat QuikClot releases calcium into blood and promotes blood coagulation in vitro

PubMed Central

Li, Jing; Cao, Wei; Lv, Xiao-xing; Jiang, Li; Li, Yue-jun; Li, Wang-zhou; Chen, Shao-zong; Li, Xue-yong

2013-01-01

Aim: To examine the changes in electrolyte concentrations after addition of zeolite-based hemostat QuikClot in blood and the effects of zeolite on blood coagulation in vitro. Methods: Fresh blood was taken from healthy adult volunteers and sheep, and the electrolyte concentrations in blood were measured using a blood electrolyte analyzer. Zeolite Saline Solution (ZSS) was prepared by addition of 2 g zeolite to 0.9% NaCl solution (4, 8, or 16 mL). The electrolytes in ZSS were measured using inductively coupled plasma atomic emission spectroscopy. The prothrombin time (PT) and activated partial thromboplastin time (APTT) of blood were measured using the test tube method. The activated clotting time (ACT) and clotting rate (CR) of blood were measured with Sonoclot Coagulation and Platelet Function Analyzer. Results: Addition of zeolite (50 and 100 mg) in 2 mL human blood significantly increased Ca2+ concentration, while Na+ and K+ concentrations were significantly decreased. Addition of zeolite (50 and 100 mg) in 0.9% NaCl solution (2 mL) caused similar changes in Ca2+ and Na+ concentrations. Si4+ (0.2434 g/L) and Al3+ (0.2575 g/L) were detected in ZSS (2 g/8 mL). Addition of ZSS in sheep blood shortened APTT in a concentration dependent manner, without changing PT. ZSS or aqueous solution of CaCl2 that contained Ca2+ concentration identical to that of ZSS significantly shortened ACT in human blood without significantly changing CR, and the effect of ZSS on ACT was not significantly different from that of CaCl2. Conclusion: Zeolite releases Ca2+ into blood, thus accelerating the intrinsic pathway of blood coagulation and shortening the clot formation time. PMID:23334236

Zeolite-based hemostat QuikClot releases calcium into blood and promotes blood coagulation in vitro.

PubMed

Li, Jing; Cao, Wei; Lv, Xiao-xing; Jiang, Li; Li, Yue-jun; Li, Wang-zhou; Chen, Shao-zong; Li, Xue-yong

2013-03-01

To examine the changes in electrolyte concentrations after addition of zeolite-based hemostat QuikClot in blood and the effects of zeolite on blood coagulation in vitro. Fresh blood was taken from healthy adult volunteers and sheep, and the electrolyte concentrations in blood were measured using a blood electrolyte analyzer. Zeolite Saline Solution (ZSS) was prepared by addition of 2 g zeolite to 0.9% NaCl solution (4, 8, or 16 mL). The electrolytes in ZSS were measured using inductively coupled plasma atomic emission spectroscopy. The prothrombin time (PT) and activated partial thromboplastin time (APTT) of blood were measured using the test tube method. The activated clotting time (ACT) and clotting rate (CR) of blood were measured with Sonoclot Coagulation and Platelet Function Analyzer. Addition of zeolite (50 and 100 mg) in 2 mL human blood significantly increased Ca(2+) concentration, while Na(+) and K(+) concentrations were significantly decreased. Addition of zeolite (50 and 100 mg) in 0.9% NaCl solution (2 mL) caused similar changes in Ca(2+) and Na(+) concentrations. Si(4+) (0.2434 g/L) and Al(3+) (0.2575 g/L) were detected in ZSS (2 g/8 mL). Addition of ZSS in sheep blood shortened APTT in a concentration dependent manner, without changing PT. ZSS or aqueous solution of CaCl2 that contained Ca(2+) concentration identical to that of ZSS significantly shortened ACT in human blood without significantly changing CR, and the effect of ZSS on ACT was not significantly different from that of CaCl2. Zeolite releases Ca(2+) into blood, thus accelerating the intrinsic pathway of blood coagulation and shortening the clot formation time.

An Aqueous Redox-Flow Battery with High Capacity and Power: The TEMPTMA/MV System.

PubMed

Janoschka, Tobias; Martin, Norbert; Hager, Martin D; Schubert, Ulrich S

2016-11-07

Redox-flow batteries (RFB) can easily store large amounts of electric energy and thereby mitigate the fluctuating output of renewable power plants. They are widely discussed as energy-storage solutions for wind and solar farms to improve the stability of the electrical grid. Most common RFB concepts are based on strongly acidic metal-salt solutions or poorly performing organics. Herein we present a battery which employs the highly soluble N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TEMPTMA) and the viologen derivative N,N'-dimethyl-4,4-bipyridinium dichloride (MV) in a simple and safe aqueous solution as redox-active materials. The resulting battery using these electrolyte solutions has capacities of 54 Ah L -1 , giving a total energy density of 38 Wh L -1 at a cell voltage of 1.4 V. With peak current densities of up to 200 mA cm -2 the TEMPTMA/MV system is a suitable candidate for compact high-capacity and high-power applications. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aggregation of TiO2-graphene nanocomposites in aqueous environment: Influence of environmental factors and UV irradiation.

PubMed

Hua, Zulin; Zhang, Jianan; Bai, Xue; Ye, Zhengfang; Tang, Zhiqiang; Liang, Lu; Liu, Yuqi

2016-01-01

The aggregation kinetics of TiO2-graphene nanocomposites in aqueous solution affected by solution pH, salt types (NaCl, CaCl2) and concentrations of electrolytes, and stability induced by UV irradiation was investigated in this study. The zeta potentials and hydrodynamic diameter of the nanoparticles were used as bases to assess the aggregation behavior, and stability of nanocomposites exposed to UV irradiation was expressed in terms of supernatant concentration. The aggregation of TiO2-graphene nanoparticles in aqueous media followed the colloidal theory. TiO2-graphene nanoparticles were significantly aggregated in the presence of a diavalent cation compared with monovalent cation because the former was more capable of effective charge screening and neutralization. The calculated Hamaker constant of the TiO2-graphene nanocomposites in aqueous solution prepared in the lab was 2.31×10(-20)J. The stability of this composite nanoparticles was between those of pure TiO2 and graphene. A known intensity of UV irradiation was beneficial in the formation of TiO2-graphene nanoparticle aggregates. However, prolonged UV irradiation may stabilize the nanoparticles. These results provided critical information about the colloidal properties of the new TiO2-graphene nanocomposites and were useful in predicting the fate and transport of TiO2-graphene nanocomposites in natural water environments. Copyright © 2015 Elsevier B.V. All rights reserved.

A Brief Review on Multivalent Intercalation Batteries with Aqueous Electrolytes.

PubMed

Guduru, Ramesh K; Icaza, Juan C

2016-02-26

Rapidly growing global demand for high energy density rechargeable batteries has driven the research toward developing new chemistries and battery systems beyond Li-ion batteries. Due to the advantages of delivering more than one electron and giving more charge capacity, the multivalent systems have gained considerable attention. At the same time, affordability, ease of fabrication and safety aspects have also directed researchers to focus on aqueous electrolyte based multivalent intercalation batteries. There have been a decent number of publications disclosing capabilities and challenges of several multivalent battery systems in aqueous electrolytes, and while considering an increasing interest in this area, here, we present a brief overview of their recent progress, including electrode chemistries, functionalities and challenges.

Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice? [Metal-Air Batteries: Future Electrochemical Energy Storage of Choice?

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

Li, Yanguang; Lu, Jun

Metal-air batteries have much higher theoretical energy density than lithium-ion batteries, and are frequently advocated as the solution toward next-generation electrochemical energy storage for applications including electric vehicles or grid energy storage. Yet they have not fulfilled their full potentials as limited by challenges associated with the metal anode, air cathode and electrolyte. These challenges would have to be properly resolved before metal-air batteries can become a practical reality and be deployed on a large scale. Here we survey the current status and latest advances in metal-air battery research for both aqueous (e.g. Zn-air) and non-aqueous (e.g. Li-air) systems. Themore » general technical issues confronting their developments are overviewed, and our perspective on possible solutions is offered.« less

Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice? [Metal-Air Batteries: Future Electrochemical Energy Storage of Choice?

DOE PAGES

Li, Yanguang; Lu, Jun

2017-05-05

Metal-air batteries have much higher theoretical energy density than lithium-ion batteries, and are frequently advocated as the solution toward next-generation electrochemical energy storage for applications including electric vehicles or grid energy storage. Yet they have not fulfilled their full potentials as limited by challenges associated with the metal anode, air cathode and electrolyte. These challenges would have to be properly resolved before metal-air batteries can become a practical reality and be deployed on a large scale. Here we survey the current status and latest advances in metal-air battery research for both aqueous (e.g. Zn-air) and non-aqueous (e.g. Li-air) systems. Themore » general technical issues confronting their developments are overviewed, and our perspective on possible solutions is offered.« less

The isoelectric point/point-of zero-charge of interfaces formed by aqueous solutions and nonpolar solids, liquids, and gases.

PubMed

Healy, Thomas W; Fuerstenau, Douglas W

2007-05-01

From our previous work on the role of the electrostatic field strength in controlling the pH of the iso-electric point (iep)/point-of-zero-charge (pzc) of polar solids we have extended the analysis to predict that the pH of the iep/pzc of a nonpolar solid, liquid or gas-aqueous interface should occur at pH 1.0-3.0, dependent on the value assigned to water molecules or clusters at the interface. Consideration of a wide range of experimental results covering nonpolar solids such as molybdenite, stibnite, paraffin, etc. as well as hydrocarbon liquids such as xylene, decalin, and long chain (>C8) alkane oils, as well as nitrogen and hydrogen gases, all in various simple 1:1 electrolyte solutions confirm the general validity of the result. We further consider various models of the origin of the charge on nonpolar material-water interfaces.

Method and apparatus for hydrogen production from water

NASA Technical Reports Server (NTRS)

Muradov, Nazim Z. (Inventor)

2012-01-01

A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

α,ω-dihexyl-sexithiophene thin films for solution-gated organic field-effect transistors

NASA Astrophysics Data System (ADS)

Schamoni, Hannah; Noever, Simon; Nickel, Bert; Stutzmann, Martin; Garrido, Jose A.

2016-02-01

While organic semiconductors are being widely investigated for chemical and biochemical sensing applications, major drawbacks such as the poor device stability and low charge carrier mobility in aqueous electrolytes have not yet been solved to complete satisfaction. In this work, solution-gated organic field-effect transistors (SGOFETs) based on the molecule α,ω-dihexyl-sexithiophene (DH6T) are presented as promising platforms for in-electrolyte sensing. Thin films of DH6T were investigated with regard to the influence of the substrate temperature during deposition on the grain size and structural order. The performance of SGOFETs can be improved by choosing suitable growth parameters that lead to a two-dimensional film morphology and a high degree of structural order. Furthermore, the capability of the SGOFETs to detect changes in the pH or ionic strength of the gate electrolyte is demonstrated and simulated. Finally, excellent transistor stability is confirmed by continuously operating the device over a period of several days, which is a consequence of the low threshold voltage of DH6T-based SGOFETs. Altogether, our results demonstrate the feasibility of high performance and highly stable organic semiconductor devices for chemical or biochemical applications.

Electrogenerative oxidation of lower alcohols to useful products

DOEpatents

Meshbesher, Thomas M.

1987-01-01

In the disclosed electrogenerative process for converting alcohols such as ethanol to aldehydes such as acetaldehyde, the alcohol starting material is an aqueous solution containing more than the azeotropic amount of water. Good first-pass conversions (<40% and more typically <50%) are obtained at operating cell voltages in the range of about 80 to about 350 millivolts at ordinary temperatures and pressures by using very high flow rates of alcohol to the exposed anode surface (i.e. the "gas" side of an anode whose other surface is in contact with the electrolyte). High molar flow rates of vaporized aqueous alcohol also help to keep formation of undesired byproducts at a low level.

Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

NASA Astrophysics Data System (ADS)

Marković, Radmila; Stevanović, Jasmina; Avramović, Ljiljana; Nedeljković, Dragutin; Jugović, Branimir; Stajić-Trošić, Jasna; Gvozdenović, Milica

2012-12-01

The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipitated at the bottom of the electrolytic cell. By this procedure, the content of copper could be reduced to the 20 mass pct of the initial value. Chemical characterization of the sludge has shown that it contains about 90 mass pct of copper. During the decopperization process, the very strong poison, arsine, can be formed, and the process is in that case terminated. The copper leaching degree of 82 mass pct is obtained using H2SO4 aqueous solution with the oxygen addition during the cathode sludge chemical treatment at 80 °C ± 5 °C. Obtained copper salt satisfies the requirements of the Serbian Standard for Pesticide, SRPS H.P1. 058. Therefore, the treatment of waste sulfuric acid solutions is of great economic and environmental interest.

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.

Non-aqueous electrolytes for electrochemical cells

DOEpatents

Zhang, Zhengcheng; Dong, Jian; Amine, Khalil

2016-06-14

An electrolyte electrochemical device includes an anodic material and an electrolyte, the electrolyte including an organosilicon solvent, a salt, and a hybrid additiving having a first and a second compound, the hybrid additive configured to form a solid electrolyte interphase film on the anodic material upon application of a potential to the electrochemical device.

Transformation of atmospheric components near a spark discharge at the anode polarization of a metallic electrode hanging over a solution

NASA Astrophysics Data System (ADS)

Orlov, A. M.; Yavtushenko, I. O.; Bodnarskii, D. S.

2013-03-01

The variation of the pressure of a gas phase activated by spark discharges between an aqueous electrolyte solution (liquid cathode) and a metallic electrode (anode) hanging over the solution is studied. A mathematical model of the proceeding reaction kinetics is constructed, and the variation of the partial pressures of all initial and produced components in the gas phase is calculated. Both the Faraday and non-Faraday mechanisms of gas component production from water are confirmed. It is found that a large overhanging drop responsible for additional supply of simultaneously produced H2 and O2 molecules forms rapidly at the end face of the anodically polarized electrode.

Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.

PubMed

Clark, Simon; Latz, Arnulf; Horstmann, Birger

2017-12-08

Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc-air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders-of-magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell-level performance of pH-buffered aqueous electrolytes. We apply our model to conduct the first continuum-scale simulation of secondary ZABs using aqueous ZnCl 2 -NH 4 Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine-containing solids may precipitate in addition to ZnO. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dielectrophoretic trapping of DNA-coated gold nanoparticles on silicon based vertical nanogap devices.

PubMed

Strobel, Sebastian; Sperling, Ralph A; Fenk, Bernhard; Parak, Wolfgang J; Tornow, Marc

2011-06-07

We report on the successful dielectrophoretic trapping and electrical characterization of DNA-coated gold nanoparticles on vertical nanogap devices (VNDs). The nanogap devices with an electrode distance of 13 nm were fabricated from Silicon-on-Insulator (SOI) material using a combination of anisotropic reactive ion etching (RIE), selective wet chemical etching and metal thin-film deposition. Au nanoparticles (diameter 40 nm) coated with a monolayer of dithiolated 8 base pairs double stranded DNA were dielectrophoretically trapped into the nanogap from electrolyte buffer solution at MHz frequencies as verified by scanning and transmission electron microscopy (SEM/TEM) analysis. First electrical transport measurements through the formed DNA-Au-DNA junctions partially revealed an approximately linear current-voltage characteristic with resistance in the range of 2-4 GΩ when measured in solution. Our findings point to the importance of strong covalent bonding to the electrodes in order to observe DNA conductance, both in solution and in the dry state. We propose our setup for novel applications in biosensing, addressing the direct interaction of biomolecular species with DNA in aqueous electrolyte media.

Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte.

PubMed

Luo, Jia-Yan; Cui, Wang-Jun; He, Ping; Xia, Yong-Yao

2010-09-01

Aqueous lithium-ion batteries may solve the safety problem associated with lithium-ion batteries that use highly toxic and flammable organic solvents, and the poor cycling life associated with commercialized aqueous rechargeable batteries such as lead-acid and nickel-metal hydride systems. But all reported aqueous lithium-ion battery systems have shown poor stability: the capacity retention is typically less than 50% after 100 cycles. Here, the stability of electrode materials in an aqueous electrolyte was extensively analysed. The negative electrodes of aqueous lithium-ion batteries in a discharged state can react with water and oxygen, resulting in capacity fading upon cycling. By eliminating oxygen, adjusting the pH values of the electrolyte and using carbon-coated electrode materials, LiTi(2)(PO(4))(3)/Li(2)SO(4)/LiFePO(4) aqueous lithium-ion batteries exhibited excellent stability with capacity retention over 90% after 1,000 cycles when being fully charged/discharged in 10 minutes and 85% after 50 cycles even at a very low current rate of 8 hours for a full charge/discharge offering an energy storage system with high safety, low cost, long cycling life and appropriate energy density.

Insight into capacitive performance of polyaniline/graphene oxide composites with ecofriendly binder

NASA Astrophysics Data System (ADS)

Bilal, Salma; Fahim, Muhammad; Firdous, Irum; Ali Shah, Anwar-ul-Haq

2018-03-01

The behaviour of gold electrode modified with polyaniline/graphene oxide composites (PGO) was studied for electrochemical and charge storage properties in aqueous acidic media. The surface of gold electrode was modified with aqueous slurry of PGO by using Carboxymethyl cellulose (CMC) as binder. The intercalation of polyaniline in the GO layers, synthesized by in situ polymerization was confirmed by scanning electron microscopy (SEM). The electrochemical behaviour and charge storing properties were investigated using cyclic voltammetry (CV), galvanostatic charge discharge (GCD) and electrochemical impedance spectroscopy (EIS). A high specific capacitance of 1721 F g-1 was obtained for PGO with 69.8% retention of capacitance even after 1000 voltammetric cycles in the potential range of 0-0.9 V at 20 mV s-1. EIS indicated low charge transfer resistance (Rct) and solution resistance (Rs) values of 0.51 Ω and 0.07 Ω, respectively. This good performance of PGO coated electrode is attributed to the use of CMC binder which generate a high electrode/ electrolyte contact area and short path lengths for electronic transport and electrolyte ion.

Solvothermal synthesis of gallium-indium-zinc-oxide nanoparticles for electrolyte-gated transistors.

PubMed

Santos, Lídia; Nunes, Daniela; Calmeiro, Tomás; Branquinho, Rita; Salgueiro, Daniela; Barquinha, Pedro; Pereira, Luís; Martins, Rodrigo; Fortunato, Elvira

2015-01-14

Solution-processed field-effect transistors are strategic building blocks when considering low-cost sustainable flexible electronics. Nevertheless, some challenges (e.g., processing temperature, reliability, reproducibility in large areas, and cost effectiveness) are requirements that must be surpassed in order to achieve high-performance transistors. The present work reports electrolyte-gated transistors using as channel layer gallium-indium-zinc-oxide nanoparticles produced by solvothermal synthesis combined with a solid-state electrolyte based on aqueous dispersions of vinyl acetate stabilized with cellulose derivatives, acrylic acid ester in styrene and lithium perchlorate. The devices fabricated using this approach display a ION/IOFF up to 1 × 10(6), threshold voltage (VTh) of 0.3-1.9 V, and mobility up to 1 cm(2)/(V s), as a function of gallium-indium-zinc-oxide ink formulation and two different annealing temperatures. These results validates the usage of electrolyte-gated transistors as a viable and promising alternative for nanoparticle based semiconductor devices as the electrolyte improves the interface and promotes a more efficient step coverage of the channel layer, reducing the operating voltage when compared with conventional dielectrics gating. Moreover, it is shown that by controlling the applied gate potential, the operation mechanism of the electrolyte-gated transistors can be modified from electric double layer to electrochemical doping.

A monolithic functional film of nanotubes/cellulose/ionic liquid for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Basiricò, Lucia; Lanzara, Giulia

2014-12-01

A novel monolithic, pre-fabricated, fully functional film made of a nanostructured free-standing layer is presented for a new and competitive class of easy-to-assemble flexible supercapacitors whose design is in-between the all solid state and the traditional liquid electrolyte. The film is made of two vertically aligned multi-walled carbon nanotube (VANT) electrodes that store ions, embedded-in, and monolithically interspaced by a solution of microcrystalline cellulose in a room temperature ionic liquid (RTIL) electrolyte (1-ethyl-3-methylimidazolium acetate-EMIM Ac). The fine tuning of VANTs length and electrolyte/cellulose amount leads, in a sole and continuous block, to ions storage and physical separation between the electrodes without the need of the additional separator layer that is typically used in supercapacitors. Thus, physical discontinuities that can induce disturbances to ions mobility, are fully eliminated significantly reducing the equivalent series resistance and increasing the knee frequency, hence outclassing the best supercapacitors based on VANTs and non-aqueous electrolytes. The excellent electrochemical response can also be addressed to the chosen electrolyte that, not only has the advantage of leading to a significantly simpler and more affordable fabrication procedure, but has higher ionic conductivity, lower viscosity and higher ions mobility than other electrolytes capable of dissolving cellulose.

Molecular species forming at the α-Fe2O3 nanoparticle-aqueous solution interface.

PubMed

Ali, Hebatallah; Seidel, Robert; Pohl, Marvin N; Winter, Bernd

2018-05-21

We report on electronic structure measurements of the interface between hematite nanoparticles (6 nm diameter) and aqueous solutions. Using soft X-ray photoelectron spectroscopy from a liquid microjet we detect valence and core-level photoelectrons as well as Auger electrons from liquid water, from the nanoparticle-water interface, and from the interior of the aqueous-phase nanoparticles. Most noteworthy, the method is shown to be sufficiently sensitive for the detection of adsorbed hydroxyl species, resulting from H 2 O dissociation at the nanoparticle surface in aqueous solution. We obtain signal from surface OH from resonant, non-resonant, and from so-called partial-electron-yield X-ray absorption (PEY-XA) spectra. In addition, we report resonant photoelectron measurements at the iron 2p excitation. The respective Fe iron 2p 3/2 edge (L 3 -edge) PEY-XA spectra exhibit two main absorption peaks with their energies being sensitive to the chemical environment of the Fe 3+ ions at the nanoparticle-solution interface. This manifests in the 10 D q value which is a measure of the ligand-field strength. Furthermore, an observed intensity variation of the pre-peak, when comparing the PEY-XA spectra for different iron Auger-decay channels, can be assigned to different extents of electron delocalization. From the experimental fraction of local versus non-local autoionization signals we then find a very fast, approximately 1 fs, charge transfer time from interfacial Fe 3+ into the environment. The present study, which is complementary to ambient-pressure photoemission studies on solid-electrolyte systems, also highlights the multiple aspects of photoemission that need to be explored for a full characterization of the transition-metal-oxide nanoparticle surface in aqueous phase.

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives.

PubMed

Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M; Armand, Michel; Zhou, Zhibin

2017-02-06

Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic conductivity and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.

Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia.

PubMed

Daniele, Salvatore; Baldo, M Antonietta; Bragato, Carlo; Abdelsalam, Mamdouh Elsayed; Denuault, Guy

2002-07-15

An oxidation process observed in dilute aqueous solutions of ammonia was investigated under steady-state conditions with gold microelectrodes with radii in the range 2.5-30 microm. Over the ammonia concentration range 0.1-10 mM, a well-defined voltammetric wave was observed at approximately 1.4 V versus Ag/AgCl. It was attributed to the oxidation of hydroxide ions that arise from the dissociation of the weak base. The steady-state limiting current was found to depend on the concentration of supporting electrolyte, and in solution with low electrolyte, it was enhanced by migration contribution, as expected for a negatively charged species that oxidizes on a positively charged electrode. In addition, the steady-state limiting current was proportional to both the ammonia concentration and the electrode radius. The overall electrode process was analyzed in terms of a CE mechanism (homogeneous chemical reaction preceding the heterogeneous electron transfer) with a fast chemical reaction when measurements were carried out in solutions containing NH3 at < or = 5 mM and with electrodes having a radius of > or = 5 microm. This was ascertained by comparing experimental and theoretical data obtained by simulation. The formation of the soluble complex species Au(NH3)2+ was also considered as a possible alternative to explain the presence of the oxidation wave. This process however was ruled out, as the experimental data did not fit theoretical predictions in any of the conditions employed in the investigation. Instead, the direct oxidation of NH3, probably to N2O, was invoked to explain the anomalous currents found when the CE process was strongly kinetically hindered. Throughout this study, a parallel was made between the CE mechanism investigated here and that known to occur during the hydrogen evolution reaction from weak acids.

Effect of ultrasound sonication on electroplating of iridium.

PubMed

Ohsaka, Takashi; Isaka, Motohiro; Hirano, Katsuhiko; Ohishi, Tomoji

2008-04-01

Effect of ultrasound sonication was examined on the electroplating of iridium in aqueous hexabromoiridate(III) solution. The electrodeposits were evaluated by observing the defects of the iridium deposits by means of voltammetry, in which the current-potential curves of the iridium deposits on copper were measured. Applying ultrasound sonication to the electroplating of iridium decreased the defects including the cracks in the deposit whenever the glycerol as the additives was contained or not in the electrolyte.

New Fluorinated and Sulfonated Block Copolymers Final Report

DTIC Science & Technology

2009-04-23

use polymers namely, Polymer Electrolyte Membrane Fuel Cells ( PEMFC ) and Direct Methanol Fuel Cells (DMFC) The DMFC can be seen as a variant of...the PEMFC . The membranes are typically the same; however, the feed for DMFC is methanol in an aqueous 1-2 M solution or in its vapor form. This fuel...the existing liquid fuels infrastructure can be used for methanol. Catalysts, as well as operating temperature ranges, are very similar to the PEMFC

Tunable reaction potentials in open framework nanoparticle battery electrodes for grid-scale energy storage.

PubMed

Wessells, Colin D; McDowell, Matthew T; Peddada, Sandeep V; Pasta, Mauro; Huggins, Robert A; Cui, Yi

2012-02-28

The electrical energy grid has a growing need for energy storage to address short-term transients, frequency regulation, and load leveling. Though electrochemical energy storage devices such as batteries offer an attractive solution, current commercial battery technology cannot provide adequate power, and cycle life, and energy efficiency at a sufficiently low cost. Copper hexacyanoferrate and nickel hexacyanoferrate, two open framework materials with the Prussian Blue structure, were recently shown to offer ultralong cycle life and high-rate performance when operated as battery electrodes in safe, inexpensive aqueous sodium ion and potassium ion electrolytes. In this report, we demonstrate that the reaction potential of copper-nickel alloy hexacyanoferrate nanoparticles may be tuned by controlling the ratio of copper to nickel in these materials. X-ray diffraction, TEM energy dispersive X-ray spectroscopy, and galvanostatic electrochemical cycling of copper-nickel hexacyanoferrate reveal that copper and nickel form a fully miscible solution at particular sites in the framework without perturbing the structure. This allows copper-nickel hexacyanoferrate to reversibly intercalate sodium and potassium ions for over 2000 cycles with capacity retentions of 100% and 91%, respectively. The ability to precisely tune the reaction potential of copper-nickel hexacyanoferrate without sacrificing cycle life will allow the development of full cells that utilize the entire electrochemical stability window of aqueous sodium and potassium ion electrolytes.

Acoustical Studies of L-leucine and L-asparagine in aqueous electrolyte through thermal expansion coefficient

NASA Astrophysics Data System (ADS)

Jajodia, S.; Chimankar, O. P.; Kalambe, A.; Goswami, S. G.

2012-12-01

Amino acids are the building blocks of the proteins; their study provides important information, about the behaviour of larger biomolecules such as proteins. The properties of proteins such as their structure, solubility, denaturation, etc. are greatly influenced by electrolytes. Ultrasonic velocity and density values have been used for evaluation of thermal expansion coefficient and adiabatic compressibility for ternary systems (amino acid/salt + water) namely L-leucine / L-asparagine each in 1.5 M aqueous solution of NaCl used as solvent for various concentrations and at different temperatures (298.15K - 323.15K). Present paper reports the variation of various thermoacoustical parameters such as Moelwyn-Hughes parameter (C1), Beyer's non-linearity parameter (B/A), internal pressure (Pi), fractional free volume (f), available volume (Va), repulsive exponent (n), molecular constant (r), van der Waals' constant (b), Debye temperatue (θD), etc. have been computed from the thermal expansion coefficient with the change of concentration and temperature. The variations of all these parameters have been interpreted in terms of various intermolecular interactions such as strong, weak, charge transfer, complex formation, hydrogen bonding interaction. The structure making and breaking properties of the interacting components existing in proposed ternary systems. It shows the associating and dissociating tendency of the molecules of solute in solvent.The hetromolecular interactions are present in both the ternary systems.

Elucidating the role of methyl viologen as a scavenger of photoactivated electrons from photosystem I under aerobic and anaerobic conditions.

PubMed

Bennett, Tyler; Niroomand, Hanieh; Pamu, Ravi; Ivanov, Ilia; Mukherjee, Dibyendu; Khomami, Bamin

2016-03-28

We present detailed electrochemical investigations into the role of dissolved O2 in electrolyte solutions in scavenging photoactivated electrons from a uniform photosystem I (PS I) monolayer assembled on alkanethiolate SAM (self-assembled monolayer)/Au surfaces while using methyl viologen (MV(2+)) as the redox mediator. To this end, we report results for direct measurements of light induced photocurrent from uniform monolayer assemblies of PS I on C9 alkanethiolate SAM/Au surfaces. These measurements, apart from demonstrating the ability of dissolved O2 in the electrolyte medium to act as an electron scavenger, also reveal its essential role in driving the solution-phase methyl viologen to initiate light-induced directional electron transfer from an electron donor surface (Au) via surface assembled PS I trimers. Specifically, our systematic electrochemical measurements have revealed that the dissolved O2 in aqueous electrolyte solutions form a complex intermediate species with MV that plays the essential role in mediating redox pathways for unidirectional electron transfer processes. This critical insight into the redox-mediated electron transfer pathways allows for rational design of electron scavengers through systematic tuning of mediator combinations that promote such intermediate formation. Our current findings facilitate the incorporation of PS I-based bio-hybrid constructs as photo-anodes in future photoelectrochemical cells and bio-electronic devices.

Evaluation of analytical performance for the simultaneous detection of trace Cu, Co and Ni by using liquid cathode glow discharge-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Yu, Jie; Zhang, Xiaomin; Lu, Quanfang; Sun, Duixiong; Wang, Xing; Zhu, Shuwen; Zhang, Zhichao; Yang, Wu

2018-07-01

In this paper, a novel liquid cathode glow discharge (LCGD) was established as a micro-plasma excitation source of atomic emission spectrometry (AES) for simultaneous detection of trace Cu, Co and Ni in aqueous solution. In order to evaluate the analytical performance, the operating parameters such as discharge voltage, supporting electrolyte, solution pH and flow rate were thoroughly investigated. The results showed that the optimal conditions are 640 V discharge voltage, pH = 1 HNO3 as supporting electrolyte and 4.5 mL min-1 flow rate. The R2 of Cu, Co and Ni are 0.9977, 0.9991 and 0.9977, respectively. The relative standard deviation (RSD) is 1.4% for Cu, 3.2% for Co and 0.8% for Ni. Under this condition, the power of LCGD is below 55 W and the plasma is quite stable. The limits of detections (LODs) for Cu, Co and Ni are 0.380, 0.080, and 0.740 mg L-1, respectively, which are basically consistent with the closed-type electrolyte cathode atmospheric glow discharge (ELCAD). Compared with ICP-AES, the LCGD-AES has small size, low power consumption, no inert gas requirement and low cost in set-up. It may be developed as a portable instrument for in-site and real-time monitoring of metals in solution samples with further improvement.

Titania nanotube powders obtained by rapid breakdown anodization in perchloric acid electrolytes

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

Ali, Saima, E-mail: saima.ali@aalto.fi; Hannula, Simo-Pekka

Titania nanotube (TNT) powders are prepared by rapid break down anodization (RBA) in a 0.1 M perchloric acid (HClO{sub 4}) solution (Process 1), and ethylene glycol (EG) mixture with HClO{sub 4} and water (Process 2). A study of the as-prepared and calcined TNT powders obtained by both processes is implemented to evaluate and compare the morphology, crystal structure, specific surface area, and the composition of the nanotubes. Longer TNTs are formed in Process 1, while comparatively larger pore diameter and wall thickness are obtained for the nanotubes prepared by Process 2. The TNTs obtained by Process 1 are converted tomore » nanorods at 350 °C, while nanotubes obtained by Process 2 preserve tubular morphology till 350 °C. In addition, the TNTs prepared by an aqueous electrolyte have a crystalline structure, whereas the TNTs obtained by Process 2 are amorphous. Samples calcined till 450 °C have XRD peaks from the anatase phase, while the rutile phase appears at 550 °C for the TNTs prepared by both processes. The Raman spectra also show clear anatase peaks for all samples except the as-prepared sample obtained by Process 2, thus supporting the XRD findings. FTIR spectra reveal the presence of O-H groups in the structure for the TNTs obtained by both processes. However, the presence is less prominent for annealed samples. Additionally, TNTs obtained by Process 2 have a carbonaceous impurity present in the structure attributed to the electrolyte used in that process. While a negligible weight loss is typical for TNTs prepared from aqueous electrolytes, a weight loss of 38.6% in the temperature range of 25–600 °C is found for TNTs prepared in EG electrolyte (Process 2). A large specific surface area of 179.2 m{sup 2} g{sup −1} is obtained for TNTs prepared by Process 1, whereas Process 2 produces nanotubes with a lower specific surface area. The difference appears to correspond to the dimensions of the nanotubes obtained by the two processes. - Graphical abstract: Titania nanotube powders prepared by Process 1 and Process 2 have different crystal structure and specific surface area. - Highlights: • Titania nanotube (TNT) powder is prepared in low water organic electrolyte. • Characterization of TNT powders prepared from aqueous and organic electrolyte. • TNTs prepared by Process 1 are crystalline with higher specific surface area. • TNTs obtained by Process 2 have carbonaceous impurities in the structure.« less

Comparison of starch and gelatin hydrogels for non-toxic supercapacitor electrolytes

NASA Astrophysics Data System (ADS)

Railanmaa, Anna; Lehtimäki, Suvi; Lupo, Donald

2017-06-01

Starch and gelatin are two of the most abundantly available natural polymers. Their non-toxicity, low cost, and compatibility with aqueous solvents make them ideal for use in ubiquitous, environmentally friendly electronics systems. This work presents the results of conductivity measurements through impedance spectroscopy for gelatin- and starch-based aqueous gel electrolytes. The NaCl-based gels were physically cross-linked. The conductivity values were 84.6 mS/cm at 1.5 mol L-1 and 71.5 mS/cm at 2 mol L-1 for gelatin and starch, respectively. The mechanical properties of gelatin were found preferable to those of starch, although they deteriorated significantly when the salt concentration exceeded 2 mol L-1. The ability of the gels to successfully act as a supercapacitor electrolyte was demonstrated with printed electrodes on plastic substrate. The devices were characterized through cyclic voltammetry measurements. The results imply that these polymer gel electrolytes are very promising for replacing the traditional aqueous liquid electrolytes in supercapacitors in applications where, for example, user and environmental safety is essential.

A Brief Review on Multivalent Intercalation Batteries with Aqueous Electrolytes

PubMed Central

Guduru, Ramesh K.; Icaza, Juan C.

2016-01-01

Rapidly growing global demand for high energy density rechargeable batteries has driven the research toward developing new chemistries and battery systems beyond Li-ion batteries. Due to the advantages of delivering more than one electron and giving more charge capacity, the multivalent systems have gained considerable attention. At the same time, affordability, ease of fabrication and safety aspects have also directed researchers to focus on aqueous electrolyte based multivalent intercalation batteries. There have been a decent number of publications disclosing capabilities and challenges of several multivalent battery systems in aqueous electrolytes, and while considering an increasing interest in this area, here, we present a brief overview of their recent progress, including electrode chemistries, functionalities and challenges. PMID:28344298

Effect of concentration boundary layers on passive solute flows in a system of two polymeric membranes positioned in vertical planes.

PubMed

Slezak, Andrzej; Jasik-Slezak, Jolanta; Dworecki, Kazimierz

2003-01-01

The results of studies of influence of concentration boundary layers on passive diffusive transport in a double-membrane osmo-diffusive cell, containing a series of two (Ml and M(r)) vertically positioned, flat, microporous and symmetric polymer membranes (Nephrophane and Cellulose IMP-1) are presented in this paper. The membranes separated three compartments (l, m, r) containing binary, heterogeneous and non-ionic solutions (aqueous solutions of glucose or ethanol) or ternary non-electrolyte solutions (glucose solutions in 0.75 mol.l-1 solution of ethanol or ethanol solutions in 0.1 mol.l-1 aqueous solution of glucose). Solution concentrations fulfilled the condition C(k)l > C(k)m > C(k)r. The intermembrane compartment (m) was an infinitesimal solution layer. The volume of the m compartment and the volumes of the external (l and r) compartments fulfilled the condition Vl = Vr approximately 170 Vm. The tests were performed for configurations A and B of a double-membrane osmo-diffusive cell. In configuration A, the solution was located behind the M(r) membrane, and water was placed behind the Ml membrane, while in configuration B this sequence was reversed. The results obtained during experiment were interpreted in the categories of convective instability, which increased the value of diffusive permeability coefficient of the system: concentration boundary layer/membrane/concentration boundary layer.

Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

PubMed

Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

2005-12-08

This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

Radiofrequency Electric Field Heating of Conductive Media: Understanding Aqueous and Nanoparticle Heating Mechanisms and a Method for Heating Optimization

NASA Astrophysics Data System (ADS)

Lara, Nadia Chantal

Use of radiofrequency (RF) electric fields coupled with nanoparticles to enhance non-invasive hyperthermia in cancer cells and tumors sparked debate over the RF heating mechanisms of nanoparticles and the role of salts in heating. Under RF field exposure at 13.56 MHz, aqueous systems including electrolyte solutions, buffers, and blood, were shown to heat according to bulk material properties, regardless of composition. This universal aqueous heating behavior extended to suspensions of nanoparticles such as gold nanoparticles, full-length and ultra-short single-walled carbon nanotubes, and water-soluble fullerene derivatives. These suspensions displayed the same RF heating properties as saline solutions of the same conductivity, indicating that these nanoparticles themselves do not contribute to RF heating by any unique mechanism; rather, they modulate bulk conductivity, which in turn affects bulk RF heating. At 13.56 MHz, peak heating for an aqueous system occurs at a conductivity of 0.06 S/m, beyond which increases in conductivity result in reduced heating rates. Biologically relevant materials, such as blood, intra- and extracellular fluids, and most human tissues, exceed this peak heating conductivity, precluding the use of conductive materials for RF heating rate enhancement. Instead, kosmotropic or water-structuring materials, including sugars, glycols, zwitterionic molecules, and a water-soluble fullerene derivative, when added to blood or phosphate buffered saline reduced the bulk conductivity of these materials and enhanced their heating rates accordingly. A dielectric heating rate model taking into account the geometry of the sample under RF exposure was used to explain the experimental RF heating behavior of aqueous solutions and semi-aqueous materials, which generated distinct RF heating curves due to differences in bulk dielectric and physical properties.

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.

An Ambient Temperature Molten Sodium-Vanadium Battery with Aqueous Flowing Catholyte.

PubMed

Liu, Caihong; Shamie, Jack S; Shaw, Leon L; Sprenkle, Vincent L

2016-01-20

In this study, we have investigated the key factors dictating the cyclic performance of a new type of hybrid sodium-based flow batteries (HNFBs) that can operate at room temperature with high cell voltages (>3 V), multiple electron transfer redox reactions per active ion, and decoupled design of power and energy. HNFBs are composed of a molten Na-Cs alloy anode, flowing aqueous catholyte, and a Na-β″-Al2O3 solid electrolyte as the separator. The surface functionalization of graphite felt electrodes for the flowing aqueous catholyte has been studied for its effectiveness in enhancing V(2+)/V(3+), V(3+)/V(4+), and V(4+)/V(5+) redox couples. The V(4+)/V(5+) redox reaction has been further investigated at different cell operation temperatures for its cyclic stability and how the properties of the solid electrolyte membrane play a role in cycling. These fundamental understandings provide guidelines for improving the cyclic performance and stability of HNFBs with aqueous catholytes. We show that the HNFB with aqueous V-ion catholyte can reach high storage capacity (∼70% of the theoretical capacity) with good Coulombic efficiency (90% ± 1% in 2-30 cycles) and cyclic performance (>99% capacity retention for 30 cycles). It demonstrates, for the first time, the potential of high capacity HNFBs with aqueous catholytes, good capacity retention and long cycling life. This is also the first demonstration that Na-β″-Al2O3 solid electrolyte can be used with aqueous electrolyte at near room temperature for more than 30 cycles.

Structural rearrangement of mesostructured silica nanoparticles incorporated with ZnO catalyst and its photoactivity: Effect of alkaline aqueous electrolyte concentration

NASA Astrophysics Data System (ADS)

Jusoh, N. W. C.; Jalil, A. A.; Triwahyono, S.; Karim, A. H.; Salleh, N. F.; Annuar, N. H. R.; Jaafar, N. F.; Firmansyah, M. L.; Mukti, R. R.; Ali, M. W.

2015-03-01

ZnO-incorporated mesostructured silica nanoparticles (MSN) catalysts (ZM) were prepared by the introduction of Zn ions into the framework of MSN via a simple electrochemical system in the presence of various concentrations of NH4OH aqueous solution. The physicochemical properties of the catalysts were studied by XRD, 29Si MAS NMR, nitrogen adsorption-desorption, FE-SEM, TEM, FTIR, and photoluminescence spectroscopy. Characterization results demonstrated that the alkaline aqueous electrolyte simply generated abundant silanol groups on the surface of the catalysts as a consequence of desilication to form the hierarchical-like structure of the MSN. Subsequent restructuring of the silica network by the creation of oxygen vacancies and formation of Si-O-Zn during the electrolysis, as well as formation of new Si-O-Si bonds during calcination seemed to be the main factors that enhanced the catalytic performance of photodecolorization of methyl orange. A ZM prepared in the presence of 1.0 M NH4OH (ZM-1.0) was determined to be the most effective catalyst. The catalyst displays a higher first-order kinetics rate of 3.87 × 10-1 h-1 than unsupported ZnO (1.13 × 10-1 h-1) that prepared under the same conditions in the absence of MSN. The experiment on effect of scavengers showed that hydroxyl radicals generated from the three main sources; reduced O2 at the conduction band, decomposed water at the valence band and irradiated H2O2 in the solution, are key factors that influenced the reaction. It is also noted that the recycled ZM-1.0 catalyst maintained its activity up to five runs without serious catalyst deactivation.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials.

PubMed

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D; Schubert, Ulrich S

2015-11-05

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

NASA Astrophysics Data System (ADS)

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D.; Schubert, Ulrich S.

2015-11-01

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

Experimental studies of contact angle hysteresis phenomena on polymer surfaces – Toward the understanding and control of wettability for different applications.

PubMed

Grundke, K; Pöschel, K; Synytska, A; Frenzel, R; Drechsler, A; Nitschke, M; Cordeiro, A L; Uhlmann, P; Welzel, P B

2015-08-01

Contact angle hysteresis phenomena on polymer surfaces have been studied by contact angle measurements using sessile liquid droplets and captive air bubbles in conjunction with a drop shape method known as Axisymmetric Drop Shape Analysis - Profile (ADSA-P). In addition, commercially available sessile drop goniometer techniques were used. The polymer surfaces were characterized with respect to their surface structure (morphology, roughness, swelling) and surface chemistry (elemental surface composition, acid-base characteristics) by scanning electron microscopy (SEM), scanning force microscopy (SFM), ellipsometry, X-ray photoelectron spectroscopy (XPS) and streaming potential measurements. Heterogeneous polymer surfaces with controlled roughness and chemical composition were prepared by different routes using plasma etching and subsequent dip coating or grafting of polymer brushes, anodic oxidation of aluminium substrates coated with thin polymer films, deposition techniques to create regular patterned and rough fractal surfaces from core-shell particles, and block copolymers. To reveal the effects of swelling and reorientation at the solid/liquid interface contact angle hysteresis phenomena on polyimide surfaces, cellulose membranes, and thermo-responsive hydrogels have been studied. The effect of different solutes in the liquid (electrolytes, surfactants) and their impact on contact angle hysteresis were characterized for solid polymers without and with ionizable functional surface groups in aqueous electrolyte solutions of different ion concentrations and pH and for photoresist surfaces in cationic aqueous surfactant solutions. The work is an attempt toward the understanding of contact angle hysteresis phenomena on polymer surfaces aimed at the control of wettability for different applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

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

Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran

A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

DOE PAGES

Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; ...

2014-12-02

A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

A computer program incorporating Pitzer's equations for calculation of geochemical reactions in brines

USGS Publications Warehouse

Plummer, Niel; Parkhurst, D.L.; Fleming, G.W.; Dunkle, S.A.

1988-01-01

The program named PHRQPITZ is a computer code capable of making geochemical calculations in brines and other electrolyte solutions to high concentrations using the Pitzer virial-coefficient approach for activity-coefficient corrections. Reaction-modeling capabilities include calculation of (1) aqueous speciation and mineral-saturation index, (2) mineral solubility, (3) mixing and titration of aqueous solutions, (4) irreversible reactions and mineral water mass transfer, and (5) reaction path. The computed results for each aqueous solution include the osmotic coefficient, water activity , mineral saturation indices, mean activity coefficients, total activity coefficients, and scale-dependent values of pH, individual-ion activities and individual-ion activity coeffients , and scale-dependent values of pH, individual-ion activities and individual-ion activity coefficients. A data base of Pitzer interaction parameters is provided at 25 C for the system: Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O, and extended to include largely untested literature data for Fe(II), Mn(II), Sr, Ba, Li, and Br with provision for calculations at temperatures other than 25C. An extensive literature review of published Pitzer interaction parameters for many inorganic salts is given. Also described is an interactive input code for PHRQPITZ called PITZINPT. (USGS)

Simply enhancing throughput of free-flow electrophoresis via organic-aqueous environment for purification of weak polarity solute of phenazine-1-carboxylic acid in fermentation of Pseudomonas sp. M18.

PubMed

Yang, Jing-Hua; Shao, Jing; Wang, Hou-Yu; Dong, Jing-Yu; Fan, Liu-Yin; Cao, Cheng-Xi; Xu, Yu-Quan

2012-09-01

Herein, a simple novel free-flow electrophoresis (FFE) method was developed via introduction of organic solvent into the electrolyte system, increasing the solute solubility and throughput of the sample. As a proof of concept, phenazine-1-carboxylic acid (PCA) from Pseudomonas sp. M18 was selected as a model solute for the demonstration on feasibility of novel FFE method on account of its faint solubility in aqueous circumstance. In the developed method, the organic solvent was added into not only the sample buffer to improve the solubility of the solute, but also the background buffer to construct a uniform aqueous-organic circumstance. These factors of organic solvent percentage and types as well as pH value of background buffer were investigated for the purification of PCA in the FFE device via CE. The experiments revealed that the percentage and the types of organic solvent exerted major influence on the purification of PCA. Under the optimized conditions (30 mM phosphate buffer in 60:40 (v/v) water-methanol at an apparent pH 7.0, 3.26 mL/min background flux, 10-min residence time of injected sample, and 400 V), PCA could be continuously purified from its impurities. The flux of sample injection was 10.05 μL/min, and the recovery was up to 93.7%. An 11.9-fold improvement of throughput was found with a carrier buffer containing 40% (v/v) methanol, compared with the pure aqueous phase. The developed procedure is of evident significance for the purification of weak polarity solute via FFE. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aggregation Kinetics of Diesel Soot Nanoparticles in Wet Environments.

PubMed

Chen, Chengyu; Huang, Weilin

2017-02-21

Soot produced during incomplete combustion consists mainly of carbonaceous nanoparticles (NPs) with severe adverse environmental and health effects, and its environmental fate and transport are largely controlled by aggregation. In this study, we examined the aggregation behavior for diesel soot NPs under aqueous condition in an effort to elucidate the fundamental processes that govern soot particle-particle interactions in wet environments such as rain droplets or surface aquatic systems. The influence of electrolytes and aqueous pH on colloidal stability of these NPs was investigated by measuring their aggregation kinetics in different aqueous solution chemistries. The results showed that the NPs had negatively charged surfaces and exhibited both reaction- and diffusion-limited aggregation regimes with rates depended upon solution chemistry. The aggregation kinetics data were in good agreement with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The critical coagulation concentrations (CCC) were quantified and the Hamaker constant was derived for the soot (1.4 × 10 -20 J) using the colloidal chemistry approach. The study indicated that, depending upon local aqueous chemistry, single soot NPs could remain stable against self-aggregation in typical freshwater environments and in neutral cloud droplets but are likely to aggregate under salty (e.g., estuaries) or acidic (e.g., acid rain droplets) aquatic conditions or both.

Design rules and reality check for carbon-based ultracapacitors

NASA Astrophysics Data System (ADS)

Eisenmann, Erhard T.

1995-04-01

Design criteria for carbon-based Ultracapacitors have been determined for specified energy and power requirements, using the geometry of the components and such material properties as density, porosity and conductivity as parameters, while also considering chemical compatibility. This analysis shows that the weights of active and inactive components of the capacitor structure must be carefully balanced for maximum energy and power density. When applied to nonaqueous electrolytes, the design rules for a 5 Wh/kg device call for porous carbon with a specific capacitance of about 30 F/cu cm. This performance is not achievable with pure, electrostatic double layer capacitance. Double layer capacitance is only 5 to 30% of that observed in aqueous electrolyte. Tests also showed that nonaqueous electrolytes have a diminished capability to access micropores in activated carbon, in one case yielding a capacitance of less than 1 F/cu cm for carbon that had 100 F/cu cm in aqueous electrolyte. With negative results on nonaqueous electrolytes dominating the present study, the obvious conclusion is to concentrate on aqueous systems. Only aqueous double layer capacitors offer adequate electrostatic charging characteristics which is the basis for high power performance. There arc many opportunities for further advancing aqueous double layer capacitors, one being the use of highly activated carbon films, as opposed to powders, fibers and foams. While the manufacture of carbon films is still costly, and while the energy and power density of the resulting devices may not meet the optimistic goals that have been proposed, this technology could produce true double layer capacitors with significantly improved performance and large commercial potential.

Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System.

PubMed

Wu, Xianyong; Qi, Yitong; Hong, Jessica J; Li, Zhifei; Hernandez, Alexandre S; Ji, Xiulei

2017-10-09

Aqueous rechargeable batteries are promising solutions for large-scale energy storage. Such batteries have the merit of low cost, innate safety, and environmental friendliness. To date, most known aqueous ion batteries employ metal cation charge carriers. Here, we report the first "rocking-chair" NH 4 -ion battery of the full-cell configuration by employing an ammonium Prussian white analogue, (NH 4 ) 1.47 Ni[Fe(CN) 6 ] 0.88 , as the cathode, an organic solid, 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), as the anode, and 1.0 m aqueous (NH 4 ) 2 SO 4 as the electrolyte. This novel aqueous ammonium-ion battery demonstrates encouraging electrochemical performance: an average operation voltage of ca. 1.0 V, an attractive energy density of ca. 43 Wh kg -1 based on both electrodes' active mass, and excellent cycle life over 1000 cycles with 67 % capacity retention. Importantly, the topochemistry results of NH 4 + in these electrodes point to a new paradigm of NH 4 + -based energy storage. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charging a capacitor from an external fluctuating potential using a single conical nanopore.

PubMed

Gomez, Vicente; Ramirez, Patricio; Cervera, Javier; Nasir, Saima; Ali, Mubarak; Ensinger, Wolfgang; Mafe, Salvador

2015-04-01

We explore the electrical rectification of large amplitude fluctuating signals by an asymmetric nanostructure operating in aqueous solution. We show experimentally and theoretically that a load capacitor can be charged to voltages close to 1 V within a few minutes by converting zero time-average potentials of amplitudes in the range 0.5-3 V into average net currents using a single conical nanopore. This process suggests that significant energy conversion and storage from an electrically fluctuating environment is feasible with a nanoscale pore immersed in a liquid electrolyte solution, a system characteristic of bioelectronics interfaces, electrochemical cells, and nanoporous membranes.

Charging a Capacitor from an External Fluctuating Potential using a Single Conical Nanopore

PubMed Central

Gomez, Vicente; Ramirez, Patricio; Cervera, Javier; Nasir, Saima; Ali, Mubarak; Ensinger, Wolfgang; Mafe, Salvador

2015-01-01

We explore the electrical rectification of large amplitude fluctuating signals by an asymmetric nanostructure operating in aqueous solution. We show experimentally and theoretically that a load capacitor can be charged to voltages close to 1 V within a few minutes by converting zero time-average potentials of amplitudes in the range 0.5–3 V into average net currents using a single conical nanopore. This process suggests that significant energy conversion and storage from an electrically fluctuating environment is feasible with a nanoscale pore immersed in a liquid electrolyte solution, a system characteristic of bioelectronics interfaces, electrochemical cells, and nanoporous membranes. PMID:25830563

One-pot synthesis of carbon-coated nanosized LiTi2(PO4)3 as anode materials for aqueous lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Zhantao; Qin, Xusong; Xu, Hui; Chen, Guohua

2015-10-01

In this study, a one-pot sintering process incorporating sol-gel preparation route and in-situ carbon coating was proposed for the synthesis of carbon-coated nanosized LiTi2(PO4)3. Experimental results show that the prepared LiTi2(PO4)3 particles are of high crystallinity and well-coated by turbostratic carbon. Attributed to nanosized particles and enhanced conductivity provided by turbostratic carbon coating, the carbon-coated LiTi2(PO4)3 showed high rate performance and good cycling life in aqueous electrolyte. Particularly, the carbon-coated LiTi2(PO4)3 exhibited initial specific capacities of 103 and 89 mAh g-1, and retained 80.6% and 97% of the initial capacities after 120 cycles at 1C and 10C in aqueous electrolyte, respectively. The high rate performance and good cycling life of carbon-coated LiTi2(PO4)3 in aqueous electrolyte reveal its potential as negative electrode in aqueous lithium-ion batteries for electric vehicles and industrial-scale energy storage systems.

A potentiodynamic study of aluminum-lithium alloys in an aqueous sodium chloride environment

NASA Technical Reports Server (NTRS)

Tsao, C.-H. T.; Pizzo, P. P.

1985-01-01

The characteristics of the potentiodynamic curves for Al-Li alloys in 3.5 percent NaCl aqueous solution are explained and the electrochemical parameters of the potentiodynamic technique are correlated to observed pitting and intergranular cracking behavior. It is shown that the oxygen content of the sodium chloride electrolyte plays an important role in the electrochemical behavior of Al-Li alloys. The potentiodynamic behavior of the alloys is found to be insensitive to variation in compositional content and heat treatment, both of which affect the stress-corrosion behavior. Stringer oxide particle attack and random pitting are observed. It is shown that alternate-immersion exposure prior to potentiodynamic polarization may offer a means of assessing susceptibility to stress-corrosion cracking.

Research of the photovoltaic properties of anodized films of Sn

NASA Astrophysics Data System (ADS)

Afanasyev, D. A.; Ibrayev, N. Kh; Omarova, G. S.; Smagulov, Zh K.

2015-04-01

The results of studies of photovoltaic properties of solar cells based on porous tin oxide films, sensitized with an organic dye are presented. Porous films were prepared by electrochemical anodization of tin in alkaline electrolytes based on aqueous solution of NaOH and aqueous ammonia NH4OH. It was found that the time of anodizing of the Sn films affects on conversion efficiency of light energy into electrical energy. Increasing of the sorption time leads to an increase of the number of molecules on the surface of the porous film. For the solar cell based on tin oxide there is a strong dark current, which significantly reduces the efficiency of conversion of light energy into electrical energy.

Effect of Divalent Electrolytes on Electroosmotic Flow

NASA Astrophysics Data System (ADS)

Li, Haifeng; Gnanaprakasam, Pradeep

2005-11-01

Electroosmotic flow (EOF) is of importance in micro- and nanofluidic applications. Recent numerical results [Zheng et al. (2003) Electrophoresis 24, 3006] suggest that the addition of even trace amounts of divalent counterions can greatly affect the velocity and electric potential distribution for EOF of a nominally monovalent electrolyte solution, nearly halving the flow rate in 20 nm channels. Scaled experiments were therefore carried out for steady and fully-developed EOF of buffered aqueous mono- and divalent electrolyte mixtures through fused silica microchannels. Nano-particle image velocimetry (nPIV), based upon evanescent-wave illumination of colloidal tracers, was used to obtain velocity data within about 300 nm of the wall. In all cases, the thickness of the electric double layer, defined as the distance from the wall where the velocity and electric potential recover to 99% of their freestream values, is of O(10 nm), or much less than the channel dimension of O(10 μm). The nPIV results are compared with predictions from an asymptotic perturbation analysis.

Nanoscale heterogeneity at the aqueous electrolyte-electrode interface

NASA Astrophysics Data System (ADS)

Limmer, David T.; Willard, Adam P.

2015-01-01

Using molecular dynamics simulations, we reveal emergent properties of hydrated electrode interfaces that while molecular in origin are integral to the behavior of the system across long times scales and large length scales. Specifically, we describe the impact of a disordered and slowly evolving adsorbed layer of water on the molecular structure and dynamics of the electrolyte solution adjacent to it. Generically, we find that densities and mobilities of both water and dissolved ions are spatially heterogeneous in the plane parallel to the electrode over nanosecond timescales. These and other recent results are analyzed in the context of available experimental literature from surface science and electrochemistry. We speculate on the implications of this emerging microscopic picture on the catalytic proficiency of hydrated electrodes, offering a new direction for study in heterogeneous catalysis at the nanoscale.

Modeling and Simulation of the Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Wohr, M.; Narayanan, S. R.; Halpert, G.

1996-01-01

From intro.: The direct methanol liquid feed fuel cell uses aqueous solutions of methanol as fuel and oxygen or air as the oxidant and uses an ionically conducting polymer membrane such as Nafion(sup r)117 and the electrolyte. This type of direct oxidation cell is fuel versatile and offers significant advantages in terms of simplicity of design and operation...The present study focuses on the results of a phenomenological model based on current understanding of the various processed operating in these cells.

An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range.

PubMed

Dutcher, Cari S; Ge, Xinlei; Wexler, Anthony S; Clegg, Simon L

2013-04-18

In previous studies (Dutcher et al. J. Phys. Chem. C 2011, 115, 16474-16487; 2012, 116, 1850-1864), we derived equations for the Gibbs energy, solvent and solute activities, and solute concentrations in multicomponent liquid mixtures, based upon expressions for adsorption isotherms that include arbitrary numbers of hydration layers on each solute. In this work, the long-range electrostatic interactions that dominate in dilute solutions are added to the Gibbs energy expression, thus extending the range of concentrations for which the model can be used from pure liquid solute(s) to infinite dilution in the solvent, water. An equation for the conversion of the reference state for solute activity coefficients to infinite dilution in water has been derived. A number of simplifications are identified, notably the equivalence of the sorption site parameters r and the stoichiometric coefficients of the solutes, resulting in a reduction in the number of model parameters. Solute concentrations in mixtures conform to a modified Zdanovskii-Stokes-Robinson mixing rule, and solute activity coefficients to a modified McKay-Perring relation, when the effects of the long-range (Debye-Hückel) term in the equations are taken into account. Practical applications of the equations to osmotic and activity coefficients of pure aqueous electrolyte solutions and mixtures show both satisfactory accuracy from low to high concentrations, together with a thermodynamically reasonable extrapolation (beyond the range of measurements) to extreme concentration and to the pure liquid solute(s).

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

PubMed

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

2015-10-20

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

Black-to-Transmissive Electrochromism with Visible-to-Near-Infrared Switching of a Co(II)-Based Metallo-Supramolecular Polymer for Smart Window and Digital Signage Applications.

PubMed

Hsu, Chih-Yu; Zhang, Jian; Sato, Takashi; Moriyama, Satoshi; Higuchi, Masayoshi

2015-08-26

Black-to-transmissive electrochromism has been obtained with a Co(II)-based metallo-supramolecular polymer (polyCo). Thin films of polyCo, based on bisterpyridine ligand assembled with Co(II) metal ion, were constructed by spray casting the polymer onto ITO glass. With such simple fabricating means to form good-quality films, polyCo films show stable switching at the central metal ion of the Co(II)/Co(I) redox reaction when immersed in aqueous solution. With an increase in the pH of the aqueous electrolyte solution from neutral, the film exhibits a color response due to the interaction between the d-orbital electron and hydroxide ions affecting the d-d* transition. As a result, a nearly transparent-to-black electrochromic performance can be achieved with a transmittance difference at 550 nm of 74.3% (81.9-7.6%) in pH 13 solution. The light absorption of the film can be tuned over light regions from visible to near-infrared with a large attenuation.

Thermal and volumetric properties of complex aqueous electrolyte solutions using the Pitzer formalism - The PhreeSCALE code

NASA Astrophysics Data System (ADS)

Lach, Adeline; Boulahya, Faïza; André, Laurent; Lassin, Arnault; Azaroual, Mohamed; Serin, Jean-Paul; Cézac, Pierre

2016-07-01

The thermal and volumetric properties of complex aqueous solutions are described according to the Pitzer equation, explicitly taking into account the speciation in the aqueous solutions. The thermal properties are the apparent relative molar enthalpy (Lϕ) and the apparent molar heat capacity (Cp,ϕ). The volumetric property is the apparent molar volume (Vϕ). Equations describing these properties are obtained from the temperature or pressure derivatives of the excess Gibbs energy and make it possible to calculate the dilution enthalpy (∆HD), the heat capacity (cp) and the density (ρ) of aqueous solutions up to high concentrations. Their implementation in PHREEQC V.3 (Parkhurst and Appelo, 2013) is described and has led to a new numerical tool, called PhreeSCALE. It was tested first, using a set of parameters (specific interaction parameters and standard properties) from the literature for two binary systems (Na2SO4-H2O and MgSO4-H2O), for the quaternary K-Na-Cl-SO4 system (heat capacity only) and for the Na-K-Ca-Mg-Cl-SO4-HCO3 system (density only). The results obtained with PhreeSCALE are in agreement with the literature data when the same standard solution heat capacity (Cp0) and volume (V0) values are used. For further applications of this improved computation tool, these standard solution properties were calculated independently, using the Helgeson-Kirkham-Flowers (HKF) equations. By using this kind of approach, most of the Pitzer interaction parameters coming from literature become obsolete since they are not coherent with the standard properties calculated according to the HKF formalism. Consequently a new set of interaction parameters must be determined. This approach was successfully applied to the Na2SO4-H2O and MgSO4-H2O binary systems, providing a new set of optimized interaction parameters, consistent with the standard solution properties derived from the HKF equations.

Enhancing the stability of lithium ion Li1+x+yAlxTi2-xSiyP3-yO12 glass - ceramic conductors in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Ioanniti, Marina Maria; Tenhaeff, Wyatt E.

2017-12-01

The stability of NASICON-type conducting glass-ceramic electrolyte, Li1+x+yAlxTi2-xSiyP3-yO12 (Ohara LICGC) has been characterized after prolonged exposure to deionized water and HCl(aq) solutions supported with LiCl. X-ray diffraction shows that the bulk crystallographic structure of the LICGC membranes remains unchanged when exposed to these solutions. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of LICGC membranes immersed in deionized water remains stable over a one month period, while there is a significant increase in resistance when exposed to the acidic solutions. When exposed to pH 4 and 2 solutions for just 24 h, the resistances of the LICGC membrane increase by a factor of 8.5 and 23.5, respectively. EIS coupled with morphological characterization by scanning electron microscopy, shows that this resistance growth is due to the development of a surface layer on the LICGC membrane. However, this substantial increase in resistance can be mitigated by adding LiCl to the HCl solutions. For a pH 4 solution supported with 6.75 M LiCl, the impedance spectrum and surface morphology are qualitatively comparable to pristine, dry LICGC material, suggesting that surface layer formation was suppressed. This was also confirmed via cyclic voltammetry measurements in four-electrode electrochemical cells.

Biomaterials for the Decorporation of Sr-85 in the Rat

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

Levitskaia, Tatiana G.; Creim, Jeffrey A.; Curry, Terry L.

2010-09-01

Although four stable isotopes of strontium occur naturally, strontium-90 is produced by nuclear fission and is present in surface soil around the world as a result of fallout from atmospheric nuclear weapons tests. It can easily transfer to man in the event of a nuclear/radiological emergency or through the plant-animal-human food chain causing long-term exposures. Strontium is chemically and biologically similar to calcium, and is incorporated primarily into bone following internal deposition. Alginic acid (alginate) obtained from seaweed (kelp) extract selectively binds ingested strontium in the GI tract blocking its systemic uptake and reducing distribution to bone in rats, whilemore » other natural polysaccharides including chitosan and hyaluronic acid had little in vivo affinity for strontium. Alginate exhibits the unique ability to discriminate between strontium and calcium and has been previously shown to reduce intestinal absorption and skeletal retention of strontium without changing calcium metabolism. In our studies, the effect of commercially available alginate on strontium intestinal absorption was examined. One problem associated with alginate treatment is its limited solubility and gel formation in water. The aqueous solubility of sodium alginate was improved in a sodium chloride/sodium bicarbonate electrolyte solution containing low molecular weight polyethylene glycol (PEG). Furthermore, oral administration of the combined alginate/electrolyte//PEG solution synergistically accelerated removal of internal strontium in rats when compared to treatment with individual sodium alginate/electrolyte or electrolyte/PEG solutions. Importantly, both alginate and PEG are nontoxic, readily available materials that can be easily administered orally in case of a national emergency when potentially large numbers of the population may require medical treatment for internal depositions. Our results suggest further studies to optimize in vivo decorporation performance of engineered alginate material via modification of its chemical and physicochemical properties is warranted.« less

Aqueous dye-sensitized solar cell electrolytes based on the ferricyanide-ferrocyanide redox couple.

PubMed

Daeneke, Torben; Uemura, Yu; Duffy, Noel W; Mozer, Attila J; Koumura, Nagatoshi; Bach, Udo; Spiccia, Leone

2012-03-02

Solar energy conversion efficiencies of over 4% have been achieved in DSCs constructed with aqueous electrolytes based on the ferricyanide-ferrocyanide redox couple, thereby avoiding the use of expensive, flammable and toxic solvents. This paradigm shift was made possible by the use of a hydrophobic organic carbazole dye. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquids as electrolytes for non-aqueous solutions electrochemical supercapacitors in a temperature range of 20 °C-80 °C

NASA Astrophysics Data System (ADS)

Zhang, Lei; Tsay, Ken; Bock, Christina; Zhang, Jiujun

2016-08-01

To increase the operating temperature of the supercapacitors (SCs) without compromising their high cycle-life, several typical fluoro- and non-fluoro containing ionic liquids (EMI-mesylate, EMI-hydrogen sulfate, PP13-triflate, PP13-TFSI, and EMI-TFSI, as shown in Fig. 1) are studied as the electrolytes to prepare organic solutions for SC performance measurements using a two-electrode cell. Both cyclic voltammograms and charge/discharge curves at various temperatures such as 20, 40, 60 and 80 °C are collected. At 60 °C, the increased performance order in both rating and cyclability measurements are found to be as follows: 1) EMI-hydrogen sulfate < PP13-TFSI < EMI-mesylate < PP13-triflate < EMI-TFSI for rating; and 2) EMI-hydrogen sulfate < EMI-mesylate < PP13-Triflate < PP13-TFSI < EMI-TFSI for life-time. The fluoro-containing group of ILs, i.e., PP13-Triflate, PP13-TFSI and EMI-TFSI can give a specific capacitance between 100 and 170 F/g for various scan rates for a conventional carbon electrode, and an extended lifetime test of 10, 000 cycles with a capacitance degradation of less than 10%, indicating that these two ion liquids can be used for SC electrolytes operated at high temperature.

Fabrication of the tea saponin functionalized reduced graphene oxide for fast adsorptive removal of Cd(II) from water

NASA Astrophysics Data System (ADS)

Li, Zhigang; Liu, Zhifeng; Wu, Zhibin; Zeng, Guangming; Shao, Binbin; Liu, Yujie; Jiang, Yilin; Zhong, Hua; Liu, Yang

2018-05-01

A novel graphene-based material of tea saponin functionalized reduced graphene oxide (TS-RGO) was synthesized via a facil thermal method, and it was characterized as the absorbent for Cd(II) removal from aqueous solutions. The factors on adsorption process including solution pH, contact time, initial concentration of Cd(II) and background electrolyte cations were studied to optimize the conditions for maximum adsorption at room temperature. The results indicated that Cd(II) adsorption was strongly dependent on pH and could be strongly affected by background electrolytes and ionic strength. The optimal pH and required equilibrium time was 6.0 and 10 min, respectively. The Cd(II) removal decreased with the presence of background electrolyte cations (Na+ < Ca2+ < Al3+). The adsorption kinetics of Cd(II) followed well with the pseudo-second-order model. The adsorption isotherm fitted well to the Langmuir model, indicating that the adsorption was a monolayer adsorption process occurred on the homogeneous surfaces of TS-RGO. The maximum monolayer adsorption capacity was 127 mg/g at 313 K and pH 6.0. Therefore, the TS-RGO was considered to be a cost-effective and promising material for the removal of Cd(II) from wastewater.

Hurdles to organic quinone flow cells. Electrode passivation by quinone reduction in acetonitrile Li electrolytes

NASA Astrophysics Data System (ADS)

Rueda-García, D.; Dubal, D. P.; Huguenin, F.; Gómez-Romero, P.

2017-05-01

The uses of quinones in Redox Flow Batteries (RFBs) has been mainly circumscribed to aqueous solutions (of derivatives with polar groups) despite a larger solubility and wider electrochemical window provided by organic media. The redox mechanism of quinones in protic media is simpler and better known than in aprotic media, where radical species are involved. This paper reports the behaviour of methyl-p-benzoquinone (MBQ) under electrochemical reduction conditions in a LiClO4sbnd CH3CN electrolyte and various working electrodes. We detected the reversible generation of a bright green coating on the working electrode and the subsequent formation of a polymer (the nature of which depends on the presence or absence of oxygen). These coatings prevent the regular redox process of methyl-p-benzoquinone from taking place on the surface of the electrode and is generated regardless of the electrode material used or the presence of O2 in solution. In addition to MBQ, the green passivating layer was also found for less sterically hindered quinones such as p-benzoquinone or 1,4-naphthoquinone, but not for anthraquinone. We have also shown the central role of Li+ in the formation of this green layer. This work provides important guidelines for the final use of quinones in RFBs with organic electrolytes.

Interruption of Hydrogen Bonding Networks of Water in Carbon Nanotubes Due to Strong Hydration Shell Formation.

PubMed

Oya, Yoshifumi; Hata, Kenji; Ohba, Tomonori

2017-10-24

We present the structures of NaCl aqueous solution in carbon nanotubes with diameters of 1, 2, and 3 nm based on an analysis performed using X-ray diffraction and canonical ensemble Monte Carlo simulations. Anomalously longer nearest-neighbor distances were observed in the electrolyte for the 1-nm-diameter carbon nanotubes; in contrast, in the 2 and 3 nm carbon nanotubes, the nearest-neighbor distances were shorter than those in the bulk electrolyte. We also observed similar properties for water in carbon nanotubes, which was expected because the main component of the electrolyte was water. However, the nearest-neighbor distances of the electrolyte were longer than those of water in all of the carbon nanotubes; the difference was especially pronounced in the 2-nm-diameter carbon nanotubes. Thus, small numbers of ions affected the entire structure of the electrolyte in the nanopores of the carbon nanotubes. The formation of strong hydration shells between ions and water molecules considerably interrupted the hydrogen bonding between water molecules in the nanopores of the carbon nanotubes. The hydration shell had a diameter of approximately 1 nm, and hydration shells were thus adopted for the nanopores of the 2-nm-diameter carbon nanotubes, providing an explanation for the large difference in the nearest-neighbor distances between the electrolyte and water in these nanopores.

Changes in apparent molar water volume and DKP solubility yield insights on the Hofmeister effect.

PubMed

Payumo, Alexander Y; Huijon, R Michael; Mansfield, Deauna D; Belk, Laurel M; Bui, Annie K; Knight, Anne E; Eggers, Daryl K

2011-12-15

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the nonideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water.

Changes in Apparent Molar Water Volume and DKP Solubility Yield Insights on the Hofmeister Effect

PubMed Central

Payumo, Alexander Y.; Huijon, R. Michael; Mansfield, Deauna D.; Belk, Laurel M.; Bui, Annie K.; Knight, Anne E.; Eggers, Daryl K.

2011-01-01

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the non-ideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water. PMID:22029390

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-05-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Capillary electrophoresis separation of neutral organic compounds, pharmaceutical drugs, proteins and peptides, enantiomers, and anions

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

Ding, Wei -Liang

1999-02-12

Addition of a novel anionic surfactant, namely lauryl polyoxyethylene sulfate, to an aqueous-acetonitrile electrolyte makes it possible to separate nonionic organic compounds by capillary electrophoresis. Separation is based on differences in the association between analytes and the surfactant. Highly hydrophobic compounds such as polyaromatic hydrocarbons are well separated by this new surfactant. Migration times of analytes can be readily changed over an unusually large range by varying the additive concentration and the proportion of acetonitrile in the electrolyte. Several examples are given, including the separation of four methylbenz[a]anthracene isomers and the separation of normal and deuterated acetophenone. The effect ofmore » adding this new surfactant to the acidic electrolyte was also investigated. Incorporation of cetyltrimethylammonium bromide in the electrolyte is shown to dynamically coat the capillary and reverse electroosmotic flow. Chiral recognition mechanism is studied using novel synthetic surfactants as chiral selectors, which are made from amino acids reacting with alkyl chloroformates. A satisfactory separation of both inorganic and organic anions is obtained using electrolyte solutions as high as 5 M sodium chloride using direct photometric detection. The effect of various salts on electrophoretic and electroosmotic mobility is further discussed. Several examples are given under high-salt conditions.« less

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-04-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Solubility of lysozyme in polyethylene glycol-electrolyte mixtures: the depletion interaction and ion-specific effects.

PubMed

Boncina, Matjaz; Rescic, Jurij; Vlachy, Vojko

2008-08-01

The solubility of aqueous solutions of lysozyme in the presence of polyethylene glycol and various alkaline salts was studied experimentally. The protein-electrolyte mixture was titrated with polyethylene glycol, and when precipitation of the protein occurred, a strong increase of the absorbance at 340 nm was observed. The solubility data were obtained as a function of experimental variables such as protein and electrolyte concentrations, electrolyte type, degree of polymerization of polyethylene glycol, and pH of the solution; the last defines the net charge of the lysozyme. The results indicate that the solubility of lysozyme decreases with the addition of polyethylene glycol; the solubility is lower for a polyethylene glycol with a higher degree of polymerization. Further, the logarithm of the protein solubility is a linear function of the polyethylene glycol concentration. The process is reversible and the protein remains in its native form. An increase of the electrolyte (NaCl) concentration decreases the solubility of lysozyme in the presence and absence of polyethylene glycol. The effect can be explained by the screening of the charged amino residues of the protein. The solubility experiments were performed at two different pH values (pH = 4.0 and 6.0), where the lysozyme net charge was +11 and +8, respectively. Ion-specific effects were systematically investigated. Anions such as Br(-), Cl(-), F(-), and H(2)PO(4)(-) (all in combination with Na(+)), when acting as counterions to a protein with positive net charge, exhibit a strong effect on the lysozyme solubility. The differences in protein solubility for chloride solutions with different cations Cs(+), K(+), and Na(+) (coions) were much smaller. The results at pH = 4.0 show that anions decrease the lysozyme solubility in the order F(-) < H(2)PO(4)(-) < Cl(-) < Br(-) (the inverse Hofmeister series), whereas cations follow the direct Hofmeister series (Cs(+) < K(+) < Na(+)) in this situation.

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol.

PubMed

Cirtiu, Ciprian Mihai; Hassani, Hicham Oudghiri; Bouchard, Nicolas-Alexandre; Rowntree, Paul A; Ménard, Hugues

2006-07-04

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.

The effect of relative solubility on crystal purity

NASA Astrophysics Data System (ADS)

Givand, Jeffrey Christopher

This study establishes the relationship between impurity incorporation in a crystal by lattice substitution and the solubility of that impurity in solution. The model system studied was L-isoleucine crystals contaminated by the isomorphic impurity L-leucine. Upon crystallization from aqueous solution by cooling, leucine is concentrated in the isoleucine unit cell through lattice substitution mechanisms. Attempts to reduce the degree of leucine incorporation via adjustments of the rate at which supersaturation is generated yielded marginal success. This work demonstrates that incorporation of leucine in the crystal can be considerably suppressed by reducing the solubility of product relative to the solubility of impurity. Changes to the relative solubility of the impurity were accomplished by the addition of various electrolytes and organic co-solvents to the aqueous amino acid solutions. The solubilities of the two amino acids were measured and compared to their solubilities in pure water. Changes in the ratio of pure-component solubilities were directly related to changes in crystal purity. This thermodynamic quantity of relative solubility was shown to be a key factor in determining impurity uptake by lattice substitution. In addition to the experimental observations, a fundamental thermodynamic link between relative solubility and crystal purity is established through this research. First, the amino acid solubility data as a function of temperature in all solvent mixtures were accurately correlated using a thermodynamic model. The parameters from this model were then adapted to a novel solid-solution thermodynamic model to express the crystal purity in terms of equilibrium solution impurity concentration. After the determination of one system specific parameter, the model is able to predict the crystal purity in a new solvent in which the pure-component solubilities are known. The ability of an electrolyte or co-solvent to improve crystal purity from a given level can now be determined based on existing solubility and purity measurements and solubilities of the product and impurity in the new solvent mixture.

Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

PubMed Central

Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

2015-01-01

Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

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

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Monovalent Ions and Water Dipoles in Contact with Dipolar Zwitterionic Lipid Headgroups-Theory and MD Simulations

PubMed Central

Velikonja, Aljaž; Perutkova, Šarka; Gongadze, Ekaterina; Kramar, Peter; Polak, Andraž; Maček-Lebar, Alenka; Iglič, Aleš

2013-01-01

The lipid bilayer is a basic building block of biological membranes and can be pictured as a barrier separating two compartments filled with electrolyte solution. Artificial planar lipid bilayers are therefore commonly used as model systems to study the physical and electrical properties of the cell membranes in contact with electrolyte solution. Among them the glycerol-based polar phospholipids which have dipolar, but electrically neutral head groups, are most frequently used in formation of artificial lipid bilayers. In this work the electrical properties of the lipid layer composed of zwitterionic lipids with non-zero dipole moments are studied theoretically. In the model, the zwitterionic lipid bilayer is assumed to be in contact with aqueous solution of monovalent salt ions. The orientational ordering of water, resulting in spatial variation of permittivity, is explicitly taken into account. It is shown that due to saturation effect in orientational ordering of water dipoles the relative permittivity in the zwitterionic headgroup region is decreased, while the corresponding electric potential becomes strongly negative. Some of the predictions of the presented mean-field theoretical consideration are critically evaluated using the results of molecular dynamics (MD) simulation. PMID:23434651

Tuning the Hydration and Lubrication of the Embedded Load-Bearing Hydrogel Fibers.

PubMed

Zhang, Ran; Feng, Yange; Ma, Shuanhong; Cai, Meirong; Yang, Jun; Yu, Bo; Zhou, Feng

2017-03-07

One of the most prominent properties of hydrogels is their excellent hydrolubrication that derives from the strong hydration of the gel network. However, excessive hydration makes hydrogels exhibit a very poor mechanical property, which limits their practical applications. Here, we prepared a novel composite surface of hydrogel nanofibers embedded in an anodic aluminum oxide substrate which exhibited both excellent lubrication and a high load-bearing capacity. Through the copolymerization of acrylic acid and 3-sulfopropyl methacrylate potassium salt, the gel network swelled sufficiently in aqueous solution and caused high osmotic pressure repulsion to bear heavy loads and hence exhibited excellent aqueous lubrication (μ ≈ 0.01). Notably, the friction coefficient of gels showed no dependence on the load in the experiment, whereas it was strongly influenced by the sliding velocity. Additionally, both electrolyte solution and ionic surfactants affect the conformation of the polymer chains, which results in a significant impact on the friction properties of hydrogel fibers.

Enhanced electrochemical performance of monoclinic WO3 thin film with redox additive aqueous electrolyte.

PubMed

Shinde, Pragati A; Lokhande, Vaibhav C; Chodankar, Nilesh R; Ji, Taeksoo; Kim, Jin Hyeok; Lokhande, Chandrakant D

2016-12-01

To achieve the highest electrochemical performance for supercapacitor, it is very essential to find out a suitable pair of an active electrode material and an electrolyte. In the present work, a simple approach is employed to enhance the supercapacitor performance of WO3 thin film. The WO3 thin film is prepared by a simple and cost effective chemical bath deposition method and its electrochemical performance is tested in conventional (H2SO4) and redox additive [H2SO4+hydroquinone (HQ)] electrolytes. Two-fold increment in electrochemical performance for WO3 thin film is observed in redox additive aqueous electrolyte compared to conventional electrolyte. WO3 thin film showed maximum specific capacitance of 725Fg(-1), energy density of 25.18Whkg(-1) at current density of 7mAcm(-2) with better cycling stability in redox electrolyte. This strategy provides the versatile way for designing the high performance energy storage devices. Copyright © 2016 Elsevier Inc. All rights reserved.

H+ diffusion and electrochemical stability of Li1+x+yAlxTi2-xSiyP3-yO12 glass in aqueous Li/air battery electrolytes

NASA Astrophysics Data System (ADS)

Ding, Fei; Xu, Wu; Shao, Yuyan; Chen, Xilin; Wang, Zhiguo; Gao, Fei; Liu, Xingjiang; Zhang, Ji-Guang

2012-09-01

It is well known that LATP (Li1+x+yAlxTi2-xSiyP3-yO12) glass is a good lithium (Li)-ion conductor. However, the interaction between LATP glass and H+ ions in aqueous electrolytes (including the diffusion and surface adsorption of H+ ions) needs to be well understood before the long-term application of LATP glass in an aqueous electrolyte can be realized. In this work, we investigate H+-ion diffusion in LATP glass and their interactions with the glass surface using both experimental and modeling approaches. Our results indicate that the apparent H+-related current observed in the initial cyclic voltammetry scan should be attributed to the adsorption of H+ ions on the LATP glass rather than the bulk diffusion of H+ ions. Furthermore, density functional theory calculations indicate that the H+-ion diffusion energy barrier (3.21 eV) is much higher than that for Li+ ions (0.79 eV) and Na+ ions (0.79 eV) in a NASICON-type LiTi2(PO4)3 material. As a result, H+-ion conductivity in LATP glass is negligible at room temperature. However, significant surface corrosion was found after the LATP glass in a strong alkaline electrolyte. Therefore, to prevent LATP glass from corrosion, appropriate electrolytes must be developed for long-term operation of LATP in aqueous Li-air batteries.

Negative differential electrolyte resistance in a solid-state nanopore resulting from electroosmotic flow bistability.

PubMed

Luo, Long; Holden, Deric A; White, Henry S

2014-03-25

A solid-state nanopore separating two aqueous solutions containing different concentrations of KCl is demonstrated to exhibit negative differential resistance (NDR) when a constant pressure is applied across the nanopore. NDR refers to a decrease in electrical current when the voltage applied across the nanopore is increased. NDR results from the interdependence of solution flow (electroosmotic and pressure-engendered) with the distributions of K+ and Cl- within the nanopore. A switch from a high-conductivity state to a low-conductivity state occurs over a very narrow voltage window (<2 mV) that depends on the nanopore geometry, electrolyte concentration, and nanopore surface charge density. Finite element simulations based on a simultaneous solution of the Navier-Stokes, Poisson, and Nernst-Planck equations demonstrate that NDR results from a positive feedback mechanism between the ion distributions and electroosmotic flow, yielding a true bistability in fluid flow and electrical current at a critical applied voltage, i.e., the NDR "switching potential". Solution pH and Ca2+ were separately employed as chemical stimuli to investigate the dependence of the NDR on the surface charge density. The NDR switching potential is remarkably sensitive to the surface charge density, and thus to pH and the presence of Ca2+, suggesting possible applications in chemical sensing.

Formation, Structure and Electrochemical Impedance Analysis of Microporous Polyelectrolyte Multilayers

NASA Astrophysics Data System (ADS)

Lutkenhaus, Jodie; McEnnis, Kathleen; Hammond, Paula

2007-03-01

Microporous networks are of interest as electrolyte materials, gas separation membranes and catalytic nanoparticle templates. Here, we create microporous polyelectrolyte networks of tunable pore size and connectivity using the layer-by-layer (LBL) technique. In this method, a film is formed from the alternate adsorption of oppositely charged polyelectrolytes from aqueous solution to create a cohesive thin film. Using poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA), LBL thin films of variable composition and charge density were assembled; then, the films were treated in an acidic bath, which ionizes PEI and de-ionizes PAA. This shift in charge density induces morphological rearrangement realized by a microporous network. Depending on the assembly pH and acidic bath pH, we are able to precisely tune the morphology, which is characterized by atomic force microscopy and scanning electron microscopy. To demonstrate the porous nature of the polyelectrolyte multilayer, the pores were filled with non-aqueous electrolyte (i.e. ethylene carbonate, dimethyl carbonate and lithium hexafluorophosphate) and probed with electrochemical impedance spectroscopy. These microporous networks exhibited two time constants, indicative of ions traveling through the liquid-filled pores and ions traveling through the polyelectrolyte matrix.

Lead-Free Sn-Ce-O Composite Coating on Cu Produced by Pulse Electrodeposition from an Aqueous Acidic Sulfate Electrolyte

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Das, Karabi; Das, Siddhartha

2017-10-01

Pulse-electrodeposited Sn-Ce-O composite solder coatings were synthesized on a Cu substrate from an aqueous acidic solution containing stannous sulfate (SnSO4·3H2O), sulfuric acid (H2SO4), and Triton X-100 as an additive. The codeposition was achieved by adding nano-cerium oxide powder in varying concentrations from 5 g/L to 20 g/L into the electrolytic bath. Microstructural characterization was carried out using x-ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy. The XRD analysis showed that the deposits consist mainly of tetragonal β (Sn) with reduced cerium oxide species. The composite coatings thus obtained exhibit a smaller grain size, possess higher microhardness, and a lower melting point than the monolithic Sn coating. The electrical resistivity of the developed composites increases, however, but lies within the permissible limits for current lead-free solder applications. Also, an optimum balance of properties in terms of microhardness, adhesion, melting point and resistivity can be obtained with 0.9 wt.% cerium oxide in the Sn matrix, which enables potential applications in solder joints and packaging.

Epitaxial Welding of Carbon Nanotube Networks for Aqueous Battery Current Collectors.

PubMed

Yao, Yonggang; Jiang, Feng; Yang, Chongyin; Fu, Kun Kelvin; Hayden, John; Lin, Chuan-Fu; Xie, Hua; Jiao, Miaolun; Yang, Chunpeng; Wang, Yilin; He, Shuaiming; Xu, Fujun; Hitz, Emily; Gao, Tingting; Dai, Jiaqi; Luo, Wei; Rubloff, Gary; Wang, Chunsheng; Hu, Liangbing

2018-05-17

Carbon nanomaterials are desirable candidates for lightweight, highly conductive, and corrosion-resistant current collectors. However, a key obstacle is their weak interconnection between adjacent nanostructures, which renders orders of magnitude lower electrical conductivity and mechanical strength in the bulk assemblies. Here we report an "epitaxial welding" strategy to engineer carbon nanotubes (CNTs) into highly crystalline and interconnected structures. Solution-based polyacrylonitrile was conformally coated on CNTs as "nanoglue" to physically join CNTs into a network, followed by a rapid high-temperature annealing (>2800 K, overall ∼30 min) to graphitize the polymer coating into crystalline layers that also bridge the adjacent CNTs to form an interconnected structure. The contact-welded CNTs (W-CNTs) exhibit both a high conductivity (∼1500 S/cm) and a high tensile strength (∼120 MPa), which are 5 and 20 times higher than the unwelded CNTs, respectively. In addition, the W-CNTs display chemical and electrochemical stabilities in strong acidic/alkaline electrolytes (>6 mol/L) when potentiostatically stressing at both cathodic and anodic potentials. With these exceptional properties, the W-CNT films are optimal as high-performance current collectors and were demonstrated in the state-of-the-art aqueous battery using a "water-in-salt" electrolyte.

Conducting polymer actuator based on chemically deposited polypyrrole and polyurethane-based solid polymer electrolyte working in air

NASA Astrophysics Data System (ADS)

Choi, Hwa-Jeong; Song, Young-Min; Chung, Ildoo; Ryu, Kwang-Sun; Jo, Nam-Ju

2009-02-01

Conducting polymers (CPs), such as polypyrrole, polythiophene, and polyaniline, are unique in that they have switchable properties due to their two or more mechanically stable oxidation states. Thus, their films or coatings can be easily switched by the application of a small voltage and current to change their volume during electrochemical redox processes. In particular, polypyrrole (PPy) has been studied most extensively because of its high electrical conductivity and good environmental stability under ambient conditions. In this work, we have studied a new CP actuator, fully polymeric, assembled with two PPy film electrodes and a solid polymer electrolyte (SPE), polyurethane/Mg(ClO4)2. Polyurethanes (PUs) were synthesized from 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (1,4-BD) and three types of polyol: poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and PPG-block-PEG-block-PPG (PPG-co-PEG). The chemical polymerization of PPy by immersion in Py monomer aqueous solution and oxidant aqueous solution is an adequate method to prepare PU/PPy composite film as an actuator. To find the proper thickness of the PPy coating layer for actuation, we measured the displacements of the actuators according to the thickness of the PPy coating layer. The displacement of all actuators is discussed in connection with the properties of the SPE and PPy. All the results obtained in this work show the feasibility of electrochemomechanical devices based on PPy and SPE film being able to work in air.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

PubMed

Azmat, Rafia; Qamar, Noshab; Naz, Raheela; Khursheed, Anum

2016-11-01

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λ max 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I 3 - ) species, instead of hypoidate (OI - ) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Aqueous corrosion and corrosion-sensitive embrittlement of Fe{sub 3}Al-based and lean-aluminum iron aluminides

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

Kim, J.G.; Buchanan, R.A.

Aqueous corrosion and corrosion-sensitive embrittlement of iron aluminides were characterized as functions of environment, alloying content, notch sensitivity, and strain rate. Polarization resistance and cyclic anodic polarization evaluations were performed in 3.5 wt % NaCl, 200 ppM Cl{sup {minus}} (pH = 4), and 1 N NaOH solutions. In the mild acid-chloride solution [200 ppM Cl{sup {minus}} (pH = 4)], the pitting-corrosion resistance of the new lean-aluminum iron aluminides (FAP-Y and CM-Mo) was comparable to that of the Fe{sub 3}Al-based FAL-Mo. In the higher-chloride 3.5 wt % NaCl, the resistance of CM-Mo was slightly less but FAP-Y showed quite similar behaviormore » to FAL-Mo. In 1 N NaOH solution, all materials exhibited ideal passive behavior. Under slow-strain-rate test conditions in the mild acid-chloride electrolyte, prior work had shown the ductilities (% elongations) of Fe{sub 3}Al-based materials to be {approximately}7% and {approximately}1% at the freely-corroding and hydrogen-charging potentials, respectively. Present studied on the lean-aluminum materials have shown the ductilities to be {approximately}17% and {approximately}5%, respectively. Thus, the present results indicate that these new materials have reasonably-good aqueous-corrosion properties in chloride environments and significantly-enhanced ductilities under aqueous corrosion conditions. The strain rate and notch sensitivities of high-aluminum iron aluminide (FA-129) were investigated by performing slow-strain-rate tests. The notch sensitivity was independent of strain rate and the notch sensitivity in the aqueous environment was similar to that in air.« less

An intrinsically self-healing NiCo//Zn rechargeable battery by self-healable ferric-ion-crosslinking sodium polyacrylate hydrogel electrolyte.

PubMed

Huang, Yan; Liu, Jie; Wang, Jiaqi; Hu, Mengmeng; Mo, Funian; Liang, Guojin; Zhi, Chunyi

2018-06-15

Self-healing solid-state aqueous rechargeable NiCo//Zn batteries are an essential element of flexible/wearable electronics due to their inherent safety, high energy density and mechanical robustness etc. However, the self-healability of solid-state batteries is only realized by few studies, in which electron/ion-inactive self-healable substrates are utilized. This fundamentally arises from the lack of self-healable electrolytes for solid-state batteries, and therefore, results in low healing efficiency and volume/mass diseconomy. Here we develop an intrinsically self-healing battery by designing a new electrolyte that is intrinsically self-healable. Sodium polyacrylate hydrogel chains are crosslinked by ferric ions to promote dynamic reconstruction of an integral network. These non-covalent crosslinkers can form ionic bonds to reconnect damaged surfaces when the hydrogel is cut off, providing an ultimate solution to the intrinsic self-healability problem of batteries. As a result, our NiCo//Zn battery with this hydrogel electrolyte can be autonomically self-healed with over 87% of capacity retained after 4 cycles of breaking/healing. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flexible asymmetric supercapacitors based upon Co9S8 nanorod//Co3O4@RuO2 nanosheet arrays on carbon cloth.

PubMed

Xu, Jing; Wang, Qiufan; Wang, Xiaowei; Xiang, Qingyi; Liang, Bo; Chen, Di; Shen, Guozhen

2013-06-25

We have successfully fabricated flexible asymmetric supercapacitors (ASCs) based on acicular Co9S8 nanorod arrays as positive materials and Co3O4@RuO2 nanosheet arrays as negative materials on woven carbon fabrics. Co9S8 nanorod arrays were synthesized by a hydrothermal sulfuration treatment of acicular Co3O4 nanorod arrays, while the RuO2 was directly deposited on the Co3O4 nanorod arrays. Carbon cloth was selected as both the substrate and the current collector for its good conductivity, high flexibility, good physical strength, and lightweight architecture. Both aqueous KOH solutions and polyvinyl alcohol (PVA)/KOH were employed as electrolyte for electrochemical measurements. The as-fabricated ASCs can be cycled reversibly in the range of 0-1.6 V and exhibit superior electrochemical performance with an energy density of 1.21 mWh/cm(3) at a power density of 13.29 W/cm(3) in aqueous electrolyte and an energy density of 1.44 mWh/cm(3) at the power density of 0.89 W/cm(3) in solid-state electrolyte, which are almost 10-fold higher than those reported in early ASC work. Moreover, they present excellent cycling performance at multirate currents and large currents after thousands of cycles. The high-performance nanostructured ASCs have significant potential applications in portable electronics and electrical vehicles.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

Solubility of carbon dioxide and hydrogen sulfide in aqueous N-methyldiethanolamine solutions

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

Huttenhuis, P.J.G.; Agrawal, N.J.; Versteeg, G.F.

2009-04-15

In this work, 72 new experimental solubility data points for H{sub 2}S and CO{sub 2} mixtures in aqueous N-methyldiethanol amine (MDEA) solutions at different methane partial pressures (up to 69 bara) are presented. They are correlated using an electrolyte equation of state (E-EOS) thermodynamic model. This model has already been used to estimate the CO{sub 2} solubility in aqueous MDEA (Huttenhuis et al. Fluid Phase Equilib. 2008, 264, 99-112) and the H{sub 2}S solubility in aqueous MDEA (Huttenhuis et al. Int. J. Oil, Gas Coal Technol. 2008, 1, 399-424). Here, the model is further extended to predict the behavior ofmore » CO{sub 2} and H{sub 2}S when they are present simultaneously in aqueous MDEA. The application of an equation of state is a new development for this type of system, i.e., of acid-gas-amine systems. The molecular interactions are described by Schwarzentruber et al.'s modification of the Redlich-Kwong-Soave equation of state, with terms added to account for ionic interactions in the liquid phase. The model is used to describe acid-gas solubility data for the CO{sub 2}-H{sub 2}S-MDEA-H{sub 2}O system reported in the open literature and experimental data reported here for the CO{sub 2}-H{sub 2}S-MDEA-H{sub 2}O-CH{sub 4} system.« less

High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

DOEpatents

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

1998-10-20

This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents. 9 figs.

Hydrate-melt electrolytes for high-energy-density aqueous batteries

NASA Astrophysics Data System (ADS)

Yamada, Yuki; Usui, Kenji; Sodeyama, Keitaro; Ko, Seongjae; Tateyama, Yoshitaka; Yamada, Atsuo

2016-10-01

Aqueous Li-ion batteries are attracting increasing attention because they are potentially low in cost, safe and environmentally friendly. However, their low energy density (<100 Wh kg-1 based on total electrode weight), which results from the narrow operating potential window of water and the limited selection of suitable negative electrodes, is problematic for their future widespread application. Here, we explore optimized eutectic systems of several organic Li salts and show that a room-temperature hydrate melt of Li salts can be used as a stable aqueous electrolyte in which all water molecules participate in Li+ hydration shells while retaining fluidity. This hydrate-melt electrolyte enables a reversible reaction at a commercial Li4Ti5O12 negative electrode with a low reaction potential (1.55 V versus Li+/Li) and a high capacity (175 mAh g-1). The resultant aqueous Li-ion batteries with high energy density (>130 Wh kg-1) and high voltage (˜2.3-3.1 V) represent significant progress towards performance comparable to that of commercial non-aqueous batteries (with energy densities of ˜150-400 Wh kg-1 and voltages of ˜2.4-3.8 V).

Effect of salts on the solubility of ionic liquids in water: experimental and electrolyte Perturbed-Chain Statistical Associating Fluid Theory†

PubMed Central

Mohammad, Sultan; Schleinitz, Miko; Coutinhoa, João A. P.; Freire, Mara G.

2016-01-01

Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg−1). At salt molalities higher than 0.2 mol kg−1, all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.20 mol kg−1. To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) was applied using ion-specific parameters. The gathered experimental data was modelled using ePC-SAFT parameters complemented by fitting a single binary parameter between K+ and the IL-ions to the IL solubility in K3PO4 aqueous solutions. Based on this approach, the description of anion-specific salting-out effects of the remaining potassium salts was found to be in good agreement with experimental data. Remarkably, ePC-SAFT is even able to predict the salting-in effect induced by K2HPO4, based on the single K+/IL-ions binary parameter which was fitted to an exclusively salting-out effect promoted by K3PO4. Finally, ePC-SAFT was applied to predict the influence of other sodium salts on the [C4C1im][NTf2] solubility in water, with experimental data taken from literature, leading to an excellent description of the liquid–liquid phase behaviour. PMID:26575280

One step effective removal of Congo Red in chitosan nanoparticles by encapsulation

NASA Astrophysics Data System (ADS)

Alver, Erol; Bulut, Mehmet; Metin, Ayşegül Ülkü; Çiftçi, Hakan

2017-01-01

Chitosan nanoparticles (CNPs) were prepared with ionotropic gelation between chitosan and tripolyphosphate for the removal of Congo Red. The production of chitosan nanoparticles and the dye removal process was carried out in one-step. The removal efficiency of Congo Red by encapsulation within chitosan from the aqueous solution and its storage stability are examined at different pH values. The influence of some parameters such as the initial dye concentration, pH value of the dye solution, electrolyte concentration, tripolyphosphate concentration, mixing time and speed on the encapsulation is examined. Congo Red removal efficiency and encapsulation capacity of chitosan nanoparticles were determined as above 98% and 5107 mg Congo Red/g chitosan, respectively.

Induced-Charge Enhancement of the Diffusion Potential in Membranes with Polarizable Nanopores

NASA Astrophysics Data System (ADS)

Ryzhkov, I. I.; Lebedev, D. V.; Solodovnichenko, V. S.; Shiverskiy, A. V.; Simunin, M. M.

2017-12-01

When a charged membrane separates two salt solutions of different concentrations, a potential difference appears due to interfacial Donnan equilibrium and the diffusion junction. Here, we report a new mechanism for the generation of a membrane potential in polarizable conductive membranes via an induced surface charge. It results from an electric field generated by the diffusion of ions with different mobilities. For uncharged membranes, this effect strongly enhances the diffusion potential and makes it highly sensitive to the ion mobilities ratio, electrolyte concentration, and pore size. Theoretical predictions on the basis of the space-charge model extended to polarizable nanopores fully agree with experimental measurements in KCl and NaCl aqueous solutions.

Solid-State Ionic Diodes Demonstrated in Conical Nanopores

DOE PAGES

Plett, Timothy S.; Cai, Wenjia; Le Thai, Mya; ...

2017-02-27

Ionic transport at the nanoscale features phenomena that are not observed in larger systems. Nonlinear current–voltage curves characteristic of ionic diodes as well as ion selectivity are examples of effects observed at the nanoscale. Many man-made nanopore systems are inspired by biological channels in a cell membrane, thus measurements are often performed in aqueous solutions. Consequently, much less is known about ionic transport in nonaqueous systems, especially in solid-state electrolytes. Here we show ionic transport through single pores filled with gel electrolyte of poly(methyl methacrylate) (PMMA) doped with LiClO 4 in propylene carbonate. The system has no liquid interface andmore » the ionic transport occurs through the porous gel structure. We demonstrate that a conically shaped nanopore filled with the gel rectifies the current and works as a solid-state ionic diode.« less

Hybrid system for rechargeable magnesium battery with high energy density

NASA Astrophysics Data System (ADS)

Chang, Zheng; Yang, Yaqiong; Wang, Xiaowei; Li, Minxia; Fu, Zhengwen; Wu, Yuping; Holze, Rudolf

2015-07-01

One of the main challenges of electrical energy storage (EES) is the development of environmentally friendly battery systems with high safety and high energy density. Rechargeable Mg batteries have been long considered as one highly promising system due to the use of low cost and dendrite-free magnesium metal. The bottleneck for traditional Mg batteries is to achieve high energy density since their output voltage is below 2.0 V. Here, we report a magnesium battery using Mg in Grignard reagent-based electrolyte as the negative electrode, a lithium intercalation compound in aqueous solution as the positive electrode, and a solid electrolyte as a separator. Its average discharge voltage is 2.1 V with stable discharge platform and good cycling life. The calculated energy density based on the two electrodes is high. These findings open another door to rechargeable magnesium batteries.

Method of preparing a sintered lithium aluminate structure for containing electrolyte

DOEpatents

Sim, James W.; Kinoshita, Kimio

1981-01-01

A porous sintered tile is formed of lithium aluminate for retaining molten lectrolyte within a fuel cell. The tile is prepared by reacting lithium hydroxide in aqueous solution with alumina particles to form beta lithium aluminate particles. The slurry is evaporated to dryness and the solids dehydrated to form a beta lithium aluminate powder. The powder is compacted into the desired shape and sintered at a temperature in excess of 1200 K. but less than 1900 K. to form a porous integral structure that is subsequently filled with molten electrolyte. A tile of this type is intended for use in containing molten alkali metal carbonates as electolyte for use in a fuel cell having porous metal or metal oxide electrodes for burning a fuel gas such as hydrogen and/or carbon monoxide with an oxidant gas containing oxygen.

pH-dependent electron-transport properties of carbon nanotubes.

PubMed

Back, Ju Hee; Shim, Moonsub

2006-11-30

Carbon nanotube electrochemical transistors integrated with microfluidic channels are utilized to examine the effects of aqueous electrolyte solutions on the electron-transport properties of single isolated carbon nanotubes. In particular, pH and concentration of supporting inert electrolytes are examined. A systematic threshold voltage shift with pH is observed while the transconductance and subthreshold swing remain independent of pH and concentration. Decreasing pH leads to a negative shift of the threshold voltage, indicating that protonation does not lead to hole doping. Changing the type of contact metal does not alter the observed pH response. The pH-dependent charging of SiO2 substrate is ruled out as the origin based on measurements with suspended nanotube transistors. Increasing the ionic strength leads to reduced pH response. Contributions from possible surface chargeable chemical groups are considered.

Nonfaradaic nanoporous electrochemistry for conductometry at high electrolyte concentration.

PubMed

Bae, Je Hyun; Kang, Chung Mu; Choi, Hyoungseon; Kim, Beom Jin; Jang, Woohyuk; Lim, Sung Yul; Kim, Hee Chan; Chung, Taek Dong

2015-02-17

Nanoporous electrified surfaces create a unique nonfaradaic electrochemical behavior that is sensitively influenced by pore size, morphology, ionic strength, and electric field modulation. Here, we report the contributions of ion concentration and applied ac frequency to the electrode impedance through an electrical double layer overlap and ion transport along the nanopores. Nanoporous Pt with uniform pore size and geometry (L2-ePt) responded more sensitively to conductivity changes in aqueous solutions than Pt black with poor uniformity despite similar real surface areas and enabled the previously difficult quantitative conductometry measurements at high electrolyte concentrations. The nanopores of L2-ePt were more effective in reducing the electrode impedance and exhibited superior linear responses to not only flat Pt but also Pt black, leading to successful conductometric detection in ion chromatography without ion suppressors and at high ionic strengths.

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

DOEpatents

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

1998-01-01

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

A new type of high energy asymmetric capacitor with nanoporous carbon electrodes in aqueous electrolyte

NASA Astrophysics Data System (ADS)

Khomenko, V.; Raymundo-Piñero, E.; Béguin, F.

A new type of low cost and high energy asymmetric capacitor based on only activated carbons for both electrodes has been developed in a safe and environment friendly aqueous electrolyte. In such electrolyte, the charges are stored in the electrical double-layer and through fast faradaic charge transfer processes. By taking profit of different redox reactions occurring in the positive and negative ranges of potential, it is possible to optimize the capacitor either by balancing the mass of the electrodes or by using different optimized carbons for the positive and negative electrodes. The best results are obtained in the latter case, by utilizing different pseudo-faradaic properties of carbons in order to increase the capacitance and to shift the potentials of water decomposition and destructive oxidation of activated carbon to more negative and positive values, respectively. After an additional adjustment of potentials by mass-balancing the two electrodes, the electrochemical capacitor can be reversibly charged/discharged at 1.6 V in aqueous medium, with energy densities close to the values obtained with electrical double-layer capacitors working in organic electrolytes, while avoiding their disadvantages.

Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

DOEpatents

Isenberg, A.O.

1987-03-10

Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection. 1 fig.

Direct Solar Charging of an Organic–Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode

PubMed Central

Wedege, Kristina; Azevedo, João; Khataee, Amirreza

2016-01-01

Abstract The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone‐2,7‐disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide‐hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron–hole recombination. PMID:27151516

Confocal micro-Raman spectroscopy of black soap films

NASA Astrophysics Data System (ADS)

Lecourt, B.; Capelle, F.; Adamietz, F.; Malaplate, A.; Blaudez, D.; Kellay, H.; Turlet, J. M.

1998-01-01

Black soap films from aqueous solutions of sodium dodecyl sulphate are studied by micro-Raman confocal spectroscopy. At the end of the draining process films of different thicknesses are obtained depending on the experimental conditions: Working in a closed humidified chamber leads to common black films while, under evaporation or in the presence of electrolyte, Newton black films are observed. From the Raman spectra of these films, quantitative information is deduced about the conformational and lateral order of the aliphatic surfactant chains, as well as the thickness of the residual water layer. More accurate measurements of the thickness of these ultimate films have been carried out by transmission ellipsometry and their effective refractive index measured by Brewster angle reflectivity. The thinner films present higher molecular organization and their aqueous core exhibits unusual spectral features.

Single-ion hydration thermodynamics from clusters to bulk solutions: Recent insights from molecular modeling

DOE PAGES

Vlcek, Lukas; Chialvo, Ariel A.

2016-01-03

The importance of single-ion hydration thermodynamic properties for understanding the driving forces of aqueous electrolyte processes, along with the impossibility of their direct experimental measurement, have prompted a large number of experimental, theoretical, and computational studies aimed at separating the cation and anion contributions. Here we provide an overview of historical approaches based on extrathermodynamic assumptions and more recent computational studies of single-ion hydration in order to evaluate the approximations involved in these methods, quantify their accuracy, reliability, and limitations in the light of the latest developments. Finally, we also offer new insights into the factors that influence the accuracymore » of ion–water interaction models and our views on possible ways to fill this substantial knowledge gap in aqueous physical chemistry.« less

Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

DOEpatents

Isenberg, Arnold O.

1987-01-01

Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection.

Applying Vertically Aligned Carbon Nanotubes in Energy Harvesting and Energy Storage

NASA Astrophysics Data System (ADS)

Oguntoye, Moses

This work has been a scientific inquisition into the potential of carbon nanotubes, fabricated in a vertically aligned configuration, for their application to solving pressing energy problems. This dissertation is introduced by providing a background to energy storage and generation as well as the various major equipment and techniques used throughout the scientific inquisition. The generic method of vertically aligned carbon nanotubes (VACNT) growth is then presented. By using a combination of recipes previously described in literature, an easy to replicate method of growing carbon nanotubes is developed with demonstrated success on different substates. The different conditions required to facilitate efficiency in the VACNT growth are highlighted. The properties of the as-grown VACNT forest are also studied and presented. Based on the recipe used, the VACNT are categorized as multiwalled and the number of walls is confirmed to be about 15 walls using transmission electron microscopy (TEM). Their graphitic nature is confirmed using thermogravimetric analysis (TGA). The surface area characterization is done using the Brunauer-Emmett-Teller (BET) method and weight-gain method. The first part of this dissertation deals with the application of the VACNT electrodes fabricated for the harvesting of mechanical energy using the triboelectric nanogenerator (TENG) technology. Here, energy is harvested from mechanical systems using both polytetrafluoroethylene (PTFE) and polyethylene (PET) counter electrodes to confirm the applicability of VACNT electrodes for this purpose. A mechanism for the electron motion is proposed based on the already identified dielectric-metal TENG pairing. Furthermore, the usefulness of this technology is demonstrated further by charging a 0.47microF capacitor to 4.5V in one minute using the VACNT-PTFE TENG. The second part of this dissertation deals with the application of VACNT electrodes in energy storage using supercapacitors. Firstly, the performance of VACNT electrodes by themselves is studied in both 3-electrode and 2-electrode systems as well as in both aqueous and organic electrolytes. Due to the larger electrochemical window possible, better performance is obtained from the system using VACNT electrodes in organic electrolyte than is obtained in aqueous electrolyte. Safety and cost limitations of the organic electrolyte forced further research into the improvement of performance in aqueous electrolyte. The solution found is to incorporate another mechanism of supercapacitive energy storage besides the formation of an electric double layer on the VACNT. This involved the uniform deposition of nickel cobaltite (a well known faradaic capacitive material) on the VACNT surface as well as using freeze-drying to preserve the vertical alignment structure. All the considerations required to achieve these goals are expressed and discussed. Overall, a comparable energy density is obtained from the aqueous electrolyte after faradaic capacitive modification of the VACNT electrode. Chapters 3 and 5 of this dissertation incorporate material in peer-reviewed journal papers published by the author.

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H(2)SO(4) in 0-3 mol kg(-1) aqueous solutions of the pure acid and to represent directly the effect of the HSO(4)(-) ↔ H(+) + SO(4)(2-) reaction. The results are incorporated into the treatment of aqueous H(2)SO(4) density described here. Densities and apparent molar volumes from -20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.

Plasma Induced Degradation of Aniline in Aqueous Solution

NASA Astrophysics Data System (ADS)

Gao, Jin-zhang; Gai, Ke; Lu, Quan-fang; Liu, Yong-jun; Wang, Xiao-yan; Deng, Hua-ling; Hu, Zhong-ai

2002-04-01

In this paper, the degradation of aniline by plasma which was generated in a localized zone between an electrolytic solution and an anode was reported. The influence of the initial concentration, temperature, pH and different mediums of aniline on the reaction kinetic was investigated. The results showed that temperature had a remarkable effect on the degradation of aniline, but the concentration had no appreciable effect on the degradation. There is a maximum elimination rate on the degradation of aniline in neutral condition. Iron (II) and other cations had a remarkable catalytic action on it. On the basis of the detailed analysis of the kinetical consideration, it was demonstrated that the oxidative degradation would be a first-order reaction. Some of the intermediate products of the degradatio process in the solution were detected by HPLC.

Surface interaction forces of cellulose nanocrystals grafted with thermoresponsive polymer brushes.

PubMed

Zoppe, Justin O; Osterberg, Monika; Venditti, Richard A; Laine, Janne; Rojas, Orlando J

2011-07-11

The colloidal stability and thermoresponsive behavior of poly(N-isopropylacrylamide) brushes grafted from cellulose nanocrystals (CNCs) of varying graft densities and molecular weights was investigated. Indication of the grafted polymer brushes was obtained after AFM imaging of CNCs adsorbed on silica. Also, aggregation of the nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of grafted CNCs in aqueous dispersions and as an ultrathin film was evaluated by using light scattering, viscosimetry, and colloidal probe microscopy (CPM). Light transmittance measurements showed temperature-dependent aggregation originating from the different graft densities and molecular weights. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength, as is the case for free poly(NiPAAm) in aqueous solution. Thermal responsive behavior of grafted CNCs in aqueous dispersions was observed by a sharp increase in dispersion viscosity as the temperature approached the LCST. CPM in liquid media for asymmetric systems consisting of ultrathin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on interaction and adhesive forces. The origin of such forces was found to be mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films were observed with the ionic strength of the aqueous solution. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as the main reasons for the less prominent polymer bridging between interacting surfaces.

Dynamics of Magnesite Formation at Low-Temperature and High pCO2 in Aqueous Solution

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

Qafoku, Odeta; Dixon, David A.; Rosso, Kevin M.

2015-09-17

Like many metal carbonate minerals, despite conditions of supersaturation, precipitation of magnesite from aqueous solution is kinetically hindered at low temperatures, for reasons that remain poorly understood. The present study examines precipitation products from reaction of Mg(OH)2 in aqueous solutions saturated with supercritical CO2 at high pressures (90 atm and 110 atm) and low temperatures (35 °C and 50 °C). Traditional bulk characterization (X-ray diffraction) of the initial solid formed indicated the presence of hydrated magnesium carbonates (hydromagnesite and nesquehonite), thermodynamically metastable phases that were found to slowly react during ageing to the more stable anhydrous form, magnesite, at temperaturesmore » as low as 35 °C (135-140 days) and at a faster rate at 50 °C (56 days). Undetected by bulk measurements, detailed examination of the precipitates by scanning electron microscopy (SEM) showed that magnesite is present as a minor component at relatively early reaction times (7 days) at 50 °C. In addition to magnesite dominating the solid phases over time, we find that mangesite nucleation and growth occurs more quickly with increasing partial pressure of CO2, and in electrolyte solutions with high bicarbonate content. Furthermore, formation of magnesite was found to be enhanced in sulfate-rich solutions, compared to chloride-rich solutions. We speculate that much of this behavior is possibly due to sulfate serving as sink of protons generated during carbonation reactions. These results support the importance of integrating magnesite as an equilibrium phase in reactive transport calculations of the effects of carbon dioxide sequestration on subsurface formations at long time scales.« less

Investigation of a chemically regenerative redox cathode polymer electrolyte fuel cell using a phosphomolybdovanadate polyoxoanion catholyte

NASA Astrophysics Data System (ADS)

Gunn, Natasha L. O.; Ward, David B.; Menelaou, Constantinos; Herbert, Matthew A.; Davies, Trevor J.

2017-04-01

Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells (PEFCs), where the direct reduction of oxygen is replaced by an in-direct mechanism occurring outside of the cell, are attractive to study as they offer a solution to the cost and durability problems faced by conventional PEFCs. This study reports the first detailed characterization of a high performance complete CRRC PEFC system, where catholyte is circulated between the cathode side of the cell and an air-liquid oxidation reactor called the "regenerator". The catholyte is an aqueous solution of phosphomolybdovanadate polyoxoanion and is assessed in terms of its performance within both a small single cell and corresponding regenerator over a range of redox states. Two methods for determining regeneration rate are proposed and explored. Expressing the regeneration rate as a "chemical" current is suggested as a useful means of measuring re-oxidation rate with respect to the cell. The analysis highlights the present limitations to the technology and provides an indication of the maximum power density achievable, which is highly competitive with conventional PEFC systems.

Improved virus inactivation using a hot bubble column evaporator (HBCE).

PubMed

Sanchis, Adrian Garrido; Shahid, Muhammad; Pashley, R M

2018-05-01

An improved hot bubble column evaporator (HBCE) was used to study virus inactivation rates using hot bubble-virus interactions in two different conditions: (1) using the bubble coalescence inhibition phenomenon of monovalent electrolytes and (2) with reducing the electrostatic repulsive forces between virus and bubble, by the addition of divalent electrolytes. It is shown that the continuous flow of (dry) air, even at 150-250 °C, only heats the aqueous solution in the bubble column to about 45°-55 °C and it was also established that viruses are not significantly affected by even long term exposure to this solution temperature, as confirmed separately from water bath experiments. Hence, the effects observed appeared to be caused entirely by collisions between the hot air bubbles and the virus organisms. It was also established that the use of high air inlet temperatures, for short periods of time, can reduce the thermal energy requirement to only about 25% (about 114 kJ/L) of that required for boiling (about 450 kJ/L). Copyright © 2018 Elsevier B.V. All rights reserved.

Transfer of highly hydrophilic ions from water to nitrobenzene, studied by three-phase and thin-film modified electrodes.

PubMed

Charreteur, Kevin; Quentel, François; Elleouet, Catherine; L'Her, Maurice

2008-07-01

The study by voltammetry of hydrophilic ion transfers across the interface between an aqueous solution and an immiscible organic solvent is limited by the presence of supporting electrolytes in both phases. Such a study is impossible for ions having a higher affinity for water than ions of the electrolytes. Indirectly, methods based on modified solid electrodes can be used; these are obtained by the deposition of an organic phase containing a molecule having redox properties, the modified electrode being in contact with an aqueous solution of the appropriate electrolyte. The three-phase electrode is very convenient for that purpose. However, this experimental tool also has its own limitation, due mainly to the redox species produced in the organic phase. The oxidized, or reduced, form of the redox molecule must have a very low affinity for water, as otherwise its transfer masks that of the ion under study. Ferrocene is almost useless because of the affinity of the ferrocenium cation for water, decamethylferrocene being a better choice. The present work illustrates how the use of lutetium bisphthalocyanines widely expands the possibilities, as these molecular sandwich complexes can be reduced as well as oxidized, the products of the reactions having a very low affinity for water. This made the determination of the Gibbs energy possible for the transfers of highly hydrophilic ions from water to nitrobenzene: Cl(-) (40 kJ mol(-1)), F(-) (57 kJ mol(-1)), H2PO4(-) (64 kJ mol(-1)). Nothing being really known about the transfer of F(-) or H2PO4(-) from water to organic solvents, these are the first values ever published. H(+), OH(-), and HSO4(-) have also been studied, showing that these species, which have a poor affinity for nitrobenzene, are prone to association reactions with the reduced or oxidized forms of the lutetium bisphthalocyanine.

Molecular Mechanisms Involved in Tissue Swelling due to Injury and due to Exposure to Low Temperature and Massive Water and Electrolyte Loss in Diarrheal Disorders.

DTIC Science & Technology

1982-10-01

to dinosaurs , they immediately were faced with - the most fundamental question, "What is a living cell?" One may well say that k the degree of our...primarily a tiny * droplet of water containing proteins and K+ saltskept apart from the body of N 0similar aqueous solution of Na salts by a microscopic...experimental evidence, besides those already mentioned, included the successful demonstration that proteins with its polypeptLde iJl existing in an extended

Physical and electrochemical characteristics of supercapacitors based on carbide derived carbon electrodes in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Eskusson, Jaanus; Jänes, Alar; Kikas, Arvo; Matisen, Leonard; Lust, Enn

FIB-SEM, XPS and gas adsorption methods have been used for the characterisation of physical properties of microporous carbide derived carbon electrodes prepared from Mo 2C at 600 °C (noted as CDC-Mo 2C). Cyclic voltammetry, constant current charge/discharge, and electrochemical impedance spectroscopy have been applied to establish the electrochemical characteristics for supercapacitors consisting of the 1 M Na 2SO 4, KOH, tetraethyl ammonium iodide or 6 M KOH aqueous electrolyte and CDC-Mo 2C electrodes. The N 2 sorption values obtained have been correlated with electrochemical characteristics for supercapacitors in various aqueous electrolytes. The maximum gravimetric energy, E max, and gravimetric power, P max, for supercapacitors (taking into consideration the active material weight) have been obtained at cell voltage 0.9 V for 6 M KOH aqueous supercapacitor (E max = 5.7 Wh kg -1 and P max = 43 kW kg -1). For 1 M TEAI based SC somewhat higher E max (6.2 Wh kg -1) and comparatively low P max (7.0 kW kg -1) have been calculated.

New-concept Batteries Based on Aqueous Li+/Na+ Mixed-ion Electrolytes

PubMed Central

Chen, Liang; Gu, Qingwen; Zhou, Xufeng; Lee, Saixi; Xia, Yonggao; Liu, Zhaoping

2013-01-01

Rechargeable batteries made from low-cost and abundant materials operating in safe aqueous electrolytes are attractive for large-scale energy storage. Sodium-ion battery is considered as a potential alternative of current lithium-ion battery. As sodium-intercalation compounds suitable for aqueous batteries are limited, we adopt a novel concept of Li+/Na+ mixed-ion electrolytes to create two batteries (LiMn2O4/Na0.22MnO2 and Na0.44MnO2/TiP2O7), which relies on two electrochemical processes. One involves Li+ insertion/extraction reaction, and the other mainly relates to Na+ extraction/insertion reaction. Two batteries exhibit specific energy of 17 Wh kg−1 and 25 Wh kg−1 based on the total weight of active electrode materials, respectively. As well, aqueous LiMn2O4/Na0.22MnO2 battery is capable of separating Li+ and Na+ due to its specific mechanism unlike the traditional “rocking-chair” lithium-ion batteries. Hence, the Li+/Na+ mixed-ion batteries offer promising applications in energy storage and Li+/Na+ separation. PMID:23736113

Chemical Thermodynamics of Aqueous Atmospheric Aerosols: Modeling and Microfluidic Measurements

NASA Astrophysics Data System (ADS)

Nandy, L.; Dutcher, C. S.

2017-12-01

Accurate predictions of gas-liquid-solid equilibrium phase partitioning of atmospheric aerosols by thermodynamic modeling and measurements is critical for determining particle composition and internal structure at conditions relevant to the atmosphere. Organic acids that originate from biomass burning, and direct biogenic emission make up a significant fraction of the organic mass in atmospheric aerosol particles. In addition, inorganic compounds like ammonium sulfate and sea salt also exist in atmospheric aerosols, that results in a mixture of single, double or triple charged ions, and non-dissociated and partially dissociated organic acids. Statistical mechanics based on a multilayer adsorption isotherm model can be applied to these complex aqueous environments for predictions of thermodynamic properties. In this work, thermodynamic analytic predictive models are developed for multicomponent aqueous solutions (consisting of partially dissociating organic and inorganic acids, fully dissociating symmetric and asymmetric electrolytes, and neutral organic compounds) over the entire relative humidity range, that represent a significant advancement towards a fully predictive model. The model is also developed at varied temperatures for electrolytes and organic compounds the data for which are available at different temperatures. In addition to the modeling approach, water loss of multicomponent aerosol particles is measured by microfluidic experiments to parameterize and validate the model. In the experimental microfluidic measurements, atmospheric aerosol droplet chemical mimics (organic acids and secondary organic aerosol (SOA) samples) are generated in microfluidic channels and stored and imaged in passive traps until dehydration to study the influence of relative humidity and water loss on phase behavior.

Toward a Molecular Understanding of Energetics in Li–S Batteries Using Nonaqueous Electrolytes: A High-Level Quantum Chemical Study

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

Assary, Rajeev S.; Curtiss, Larry A.; Moore, Jeffrey S.

2014-06-05

The Li-S battery (secondary cell or redox flow) technology is a promising future alternative to the present lithium intercalation-based energy storage and, therefore, a molecular level understanding of the chemical processes and properties such as stability of intermediates, reactivity of polysulfides and reactivity towards the non-aqueous electrolytes in the Li-S batteries is of great interest. In this paper, quantum chemical methods (G4MP2, MP2, and B3LYP) were utilized to compute reduction potentials of lithium polysulfides and polysulfide molecular clusters, energetics of disproportionation and association reactions of likely intermediates, and their reactions with ether-based electrolytes. Based on the computed reaction energetics inmore » solution, a probable mechanism during the discharge process for polysulfide anions and lithium polysulfides in solution is proposed and likely intermediates such as S42-,S32-, S22-, and S31- radical were identified. Additionally, the stability and reactivity of propylene carbonate and tetraglyme solvent molecules were assessed against the above-mentioned intermediates and other reactive species by computing the reaction energetics required to initiate the solvent decomposition reactions in solution. Calculations suggest that the propylene carbonate molecule is unstable against the polysulfide anions such as S22-, S32-, and S42- (ΔH† < 0.8 eV) and highly reactive towards Li2S2 and Li2S3. Even though the tetraglyme solvent molecule exhibits increased stability towards polysulfide anions compared to propylene carbonate, this molecule too is vulnerable to nucleophilic attack from Li2S2 and Li2S3 species in solutions. Hence, a long- term stability of the ether molecules is unlikely if high concentration of these reactive intermediates present in the Li-S energy storage systems.« less

Lithium batteries using poly(ethylene oxide)-based non-aqueous electrolytes

DOEpatents

Chen, Zonghai; Amine, Khalil

2015-09-08

Lithium-air cells employing poly(ethyleneoxide) phosphate-based electrolytes may be prepared and exhibit improved charge carrying capacity. Such PEO phosphates generally have the formulas IIa, IIb, IIc, where: ##STR00001##

Characterization of metal-supported axial injection plasma sprayed solid oxide fuel cells with aqueous suspension plasma sprayed electrolyte layers

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

A method for manufacturing metal-supported SOFCs with atmospheric plasma spraying (APS) is presented, making use of aqueous suspension feedstock for the electrolyte layer and dry powder feedstock for the anode and cathode layers. The cathode layer was deposited first directly onto a metal support, in order to minimize contact resistance, and to allow the introduction of added porosity. The electrolyte layers produced by suspension plasma spraying (SPS) were characterized in terms of thickness, permeability, and microstructure, and the impact of substrate morphology on electrolyte properties was investigated. Fuel cells produced by APS were electrochemically tested at temperatures ranging from 650 to 750 °C. The substrate morphology had little effect on open circuit voltage, but substrates with finer porosity resulted in lower kinetic losses in the fuel cell polarization.

Quadrupole terms in the Maxwell equations: Debye-Hückel theory in quadrupolarizable solvent and self-salting-out of electrolytes.

PubMed

Slavchov, Radomir I

2014-04-28

If the molecules of a given solvent possess significant quadrupolar moment, the macroscopic Maxwell equations must involve the contribution of the density of the quadrupolar moment to the electric displacement field. This modifies the Poisson-Boltzmann equation and all consequences from it. In this work, the structure of the diffuse atmosphere around an ion dissolved in quadrupolarizable medium is analyzed by solving the quadrupolar variant of the Coulomb-Ampere's law of electrostatics. The results are compared to the classical Debye-Hückel theory. The quadrupolar version of the Debye-Hückel potential of a point charge is finite even in r = 0. The ion-quadrupole interaction yields a significant expansion of the diffuse atmosphere of the ion and, thus, it decreases the Debye-Hückel energy. In addition, since the dielectric permittivity of the electrolyte solutions depends strongly on concentration, the Born energy of the dissolved ions alters with concentration, which has a considerable contribution to the activity coefficient γ± known as the self-salting-out effect. The quadrupolarizability of the medium damps strongly the self-salting-out of the electrolyte, and thus it affects additionally γ±. Comparison with experimental data for γ± for various electrolytes allows for the estimation of the quadrupolar length of water: LQ ≈ 2 Å, in good agreement with previous assessments. The effect of quadrupolarizability is especially important in non-aqueous solutions. Data for the activity of NaBr in methanol is used to determine the quadrupolarizability of methanol with good accuracy.

Rechargeable aqueous lithium-air batteries with an auxiliary electrode for the oxygen evolution

NASA Astrophysics Data System (ADS)

Sunahiro, S.; Matsui, M.; Takeda, Y.; Yamamoto, O.; Imanishi, N.

2014-09-01

A rechargeable aqueous lithium-air cell with a third auxiliary electrode for the oxygen evolution reaction was developed. The cell consists of a lithium metal anode, a lithium conducting solid electrolyte of Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12, a carbon black oxygen reduction air electrode, a RuO2 oxygen evolution electrode, and a saturated aqueous solution of LiOH with 10 M LiCl. The cell was successfully operated for several cycles at 0.64 mA cm-2 and 25 °C under air, where the capacity of air electrode was 2000 mAh gcathod-1. The cell performance was degraded gradually by cycling under open air. The degradation was reduced under CO2-free air and pure oxygen. The specific energy density was calculated to be 810 Wh kg-1 from the weight of water, lithium, oxygen, and carbon in the air electrode.

Aqueous rechargeable zinc/sodium vanadate batteries with enhanced performance from simultaneous insertion of dual carriers.

PubMed

Wan, Fang; Zhang, Linlin; Dai, Xi; Wang, Xinyu; Niu, Zhiqiang; Chen, Jun

2018-04-25

Rechargeable aqueous zinc-ion batteries are promising energy storage devices due to their high safety and low cost. However, they remain in their infancy because of the limited choice of positive electrodes with high capacity and satisfactory cycling performance. Furthermore, their energy storage mechanisms are not well established yet. Here we report a highly reversible zinc/sodium vanadate system, where sodium vanadate hydrate nanobelts serve as positive electrode and zinc sulfate aqueous solution with sodium sulfate additive is used as electrolyte. Different from conventional energy release/storage in zinc-ion batteries with only zinc-ion insertion/extraction, zinc/sodium vanadate hydrate batteries possess a simultaneous proton, and zinc-ion insertion/extraction process that is mainly responsible for their excellent performance, such as a high reversible capacity of 380 mAh g -1 and capacity retention of 82% over 1000 cycles. Moreover, the quasi-solid-state zinc/sodium vanadate hydrate battery is also a good candidate for flexible energy storage device.

All-solid-state Al-air batteries with polymer alkaline gel electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Zhao; Zuo, Chuncheng; Liu, Zihui; Yu, Ying; Zuo, Yuxin; Song, Yu

2014-04-01

Aluminum-air (Al-air) battery is one of the most promising candidates for next-generation energy storage systems because of its high capacity and energy density, and abundance. The polyacrylic acid (PAA)-based alkaline gel electrolyte is used in all-solid-state Al-air batteries instead of aqueous electrolytes to prevent leakage. The optimal gel electrolyte exhibits an ionic conductivity of 460 mS cm-1, which is close to that of aqueous electrolytes. The Al-air battery peak capacity and energy density considering only Al can reach 1166 mAh g-1-Al and 1230 mWh g-1-Al, respectively, during constant current discharge. The battery prototype also exhibits a high power density of 91.13 mW cm-2. For the battery is a laminated structure, area densities of 29.2 mAh cm-2 and 30.8 mWh cm-2 are presented to appraise the performance of the whole cell. A novel design to inhibit anodic corrosion is proposed by separating the Al anode from the gel electrolyte when not in use, thereby effectively maintaining the available capacity of the battery.

Multicomponent transport in membranes for redox flow batteries

NASA Astrophysics Data System (ADS)

Monroe, Charles

2015-03-01

Redox flow batteries (RFBs) incorporate separator membranes, which ideally prevent mixing of electrochemically active species while permitting crossover of inactive supporting ions. Understanding crossover and membrane selectivity may require multicomponent transport models that account for solute/solute interactions within the membrane, as well as solute/membrane interactions. Application of the Onsager-Stefan-Maxwell formalism allows one to account for all the dissipative phenomena that may accompany component fluxes through RFB membranes. The magnitudes of dissipative interactions (diffusional drag forces) are quantified by matching experimentally established concentration transients with theory. Such transients can be measured non-invasively using DC conductometry, but the accuracy of this method requires precise characterization of the bulk RFB electrolytes. Aqueous solutions containing both vanadyl sulfate (VOSO4) and sulfuric acid (H2SO4) are relevant to RFB technology. One of the first precise characterizations of aqueous vanadyl sulfate has been implemented and will be reported. To assess the viability of a separator for vanadium RFB applications with cell-level simulations, it is critical to understand the tendencies of various classes of membranes to absorb (uptake) active species, and to know the relative rates of active-species and supporting-electrolyte diffusion. It is also of practical interest to investigate the simultaneous diffusion of active species and supports, because interactions between solutes may ultimately affect the charge efficiency and power efficiency of the RFB system as a whole. A novel implementation of Barnes's classical model of dialysis-cell diffusion [Physics 5:1 (1934) 4-8] is developed to measure the binary diffusion coefficients and sorption equilibria for single solutes (VOSO4 or H2SO4) in porous membranes and cation-exchange membranes. With the binary diffusion and uptake measurement in hand, a computer simulation that extends the approach of Heintz, Wiedemann and Ziegler [J. Membrane Science 137:1-2 (1997) 121-132] is used to establish Onsager resistances that describe the drag forces VOSO4 and H2SO4 exert on each other as they interdiffuse. The ramifications of these interactions for different classes of membranes - and for RFB applications - will be discussed. NSF CBET-1253544.

Partially Fluorinated Solvent as a co-solvent for the Non-aqueous Electrolyte of Li/air Battery

DTIC Science & Technology

2010-11-11

ether ( MFE ) and tris(2,2,2-trifluoroethyl) phosphite (TTFP), respectively, as a co-solvent for the non-aqueous electrolyte of Li–air battery. Results...fluorinated solvents on the discharge performance of Li–air bat- tery. For this purpose, we here selectmethyl nonafluorobutyl ether ( MFE ) and tris...196, (2011) pgs. 2867-2870 14. ABSTRACT In this workwestudy methyl nonafluorobutyl ether ( MFE ) and tris(2,2,2-trifluoroethyl) phosphite (TTFP

High-Voltage Aqueous Magnesium Ion Batteries

DOE PAGES

Wang, Fei; Fan, Xiulin; Gao, Tao; ...

2017-10-04

Nonaqueous rechargeable magnesium (Mg) batteries suffer from the complicated and moisture-sensitive electrolyte chemistry. Besides electrolytes, the practicality of a Mg battery is also confined by the absence of high-performance electrode materials due to the intrinsically slow Mg 2+ diffusion in the solids. In this work, we demonstrated a rechargeable aqueous magnesium ion battery (AMIB) concept of high energy density, fast kinetics, and reversibility. Using a superconcentration approach we expanded the electrochemical stability window of the aqueous electrolyte to 2.0 V. More importantly, two new Mg ion host materials, Li superconcentration approach we expanded the electrochemical stability window of the aqueousmore » electrolyte to 2.0 V. More importantly, two new Mg ion host materials, Li 3V 2(PO 4) 3 and poly pyromellitic dianhydride, were developed and employed as cathode and anode electrodes, respectively. Based on comparisons of the aqueous and nonaqueous systems, the role of water is identified to be critical in the Mg ion mobility in the intercalation host but remaining little detrimental to its non-diffusion controlled process. Finally, compared with the previously reported Mg ion cell delivers an unprecedented high power density of 6400 W kg ion cell delivers an unprecedented high power density of 6400 W kg while retaining 92% of the initial capacity after 6000 cycles, pushing the Mg ion cell to a brand new stage.« less

High-Voltage Aqueous Magnesium Ion Batteries

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

Wang, Fei; Fan, Xiulin; Gao, Tao

Nonaqueous rechargeable magnesium (Mg) batteries suffer from the complicated and moisture-sensitive electrolyte chemistry. Besides electrolytes, the practicality of a Mg battery is also confined by the absence of high-performance electrode materials due to the intrinsically slow Mg 2+ diffusion in the solids. In this work, we demonstrated a rechargeable aqueous magnesium ion battery (AMIB) concept of high energy density, fast kinetics, and reversibility. Using a superconcentration approach we expanded the electrochemical stability window of the aqueous electrolyte to 2.0 V. More importantly, two new Mg ion host materials, Li superconcentration approach we expanded the electrochemical stability window of the aqueousmore » electrolyte to 2.0 V. More importantly, two new Mg ion host materials, Li 3V 2(PO 4) 3 and poly pyromellitic dianhydride, were developed and employed as cathode and anode electrodes, respectively. Based on comparisons of the aqueous and nonaqueous systems, the role of water is identified to be critical in the Mg ion mobility in the intercalation host but remaining little detrimental to its non-diffusion controlled process. Finally, compared with the previously reported Mg ion cell delivers an unprecedented high power density of 6400 W kg ion cell delivers an unprecedented high power density of 6400 W kg while retaining 92% of the initial capacity after 6000 cycles, pushing the Mg ion cell to a brand new stage.« less

Comparative study on the removal of COD from POME by electrocoagulation and electro-Fenton methods: Process optimization

NASA Astrophysics Data System (ADS)

Chairunnisak, A.; Arifin, B.; Sofyan, H.; Lubis, M. R.; Darmadi

2018-03-01

This research focuses on the Chemical Oxygen Demand (COD) treatment in palm oil mill effluent by electrocoagulation and electro-Fenton methods to solve it. Initially, the aqueous solution precipitates in acid condition at pH of about two. This study focuses on the palm oil mill effluent degradation by Fe electrodes in a simple batch reactor. This work is conducted by using different parameters such as voltage, electrolyte concentration of NaCl, volume of H2O2 and operation time. The processing of data resulted is by using response surface method coupled with Box-Behnken design. The electrocoagulation method results in the optimum COD reduction of 94.53% from operating time of 39.28 minutes, 20 volts, and without electrolyte concentration. For electro-Fenton process, experiment points out that voltage 15.78 volts, electrolyte concentration 0.06 M and H2O2 volume 14.79 ml with time 35.92 minutes yield 99.56% degradation. The result concluded that the electro-Fenton process was more effective to degrade COD of the palm-oil-mill effluent compared to electrocoagulation process.

Galvanic Tongue Stimulation Inhibits Five Basic Tastes Induced by Aqueous Electrolyte Solutions.

PubMed

Aoyama, Kazuma; Sakurai, Kenta; Sakurai, Satoru; Mizukami, Makoto; Maeda, Taro; Ando, Hideyuki

2017-01-01

Galvanic tongue stimulation (GTS) modulates taste sensation. However, the effect of GTS is contingent on the electrode polarity in the proximity of the tongue. If an anodal electrode is attached in the proximity of the tongue, an electrical or metallic taste is elicited. On the other hand, if only cathodal electrode is attached in the proximity of the tongue, the salty taste, which is induced by electrolyte materials, is inhibited. The mechanism of this taste inhibition is not adequately understood. In this study, we aim to demonstrate that the inhibition is cause by ions, which elicit taste and which migrate from the taste sensors on the tongue by GTS. We verified the inhibitory effect of GTS on all five basic tastes induced by electrolyte materials. This technology is effective for virtual reality systems and interfaces to support dietary restrictions. Our findings demonstrate that cathodal-GTS inhibits all the five basic tastes. The results also support our hypothesis that the effects of cathodal-GTS are caused by migrating tasting ions in the mouth.

3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

PubMed

Kang, Yu Jin; Yoo, Yongju; Kim, Woong

2016-06-08

State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics.

Treatment of PPROM with anhydramnion in humans: first experience with different amniotic fluid substitutes for continuous amnioinfusion through a subcutaneously implanted port system.

PubMed

Tchirikov, Michael; Bapayeva, Gauri; Zhumadilov, Zhaxybay Sh; Dridi, Yasmina; Harnisch, Ralf; Herrmann, Angelika

2013-11-01

This study aims to treat patients with preterm premature rupture of the membranes (PPROM) and anhydramnion using continuous amnioinfusion through a subcutaneously implanted port system. An amniotic fluid replacement port system was implanted in seven patients with PPROM and anhydramnion starting at the 20th week of gestation (range, 14-26 weeks) for long-term amnioinfusion. Saline solutions (2 L/day; Jonosteril(®), Sterofundin(®), isotonic NaCl 0.9% solution, lactated Ringer's solution) and a hypotonic aqueous composition with reduced chloride content similar to the electrolyte concentration of human amniotic fluid were used for the continuous amnioinfusion. The mean duration of the PPROM delivery interval continued for 49 days (range, 9-69 days), with 3 weeks of amnioinfusion via the port system (range, 4-49). The newborns showed no signs of lung hypoplasia. Long-term lavage of the amniotic cavity via a subcutaneously implanted port system in patients with PPROM and anhydramnion may help prolong the pregnancy and avoid fetal lung hypoplasia. A hypotonic aqueous composition with reduced chloride content similar to human amniotic fluid can be safely used for amnioinfusion. Prospective randomized studies are ongoing.

Compatibility of a Conventional Non-aqueous Magnesium Electrolyte with a High Voltage V 2O 5 Cathode and Mg Anode

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

Sa, Niya; Proffit, Danielle L.; Lipson, Albert L.

2015-08-01

A major roadblock for magnesium ion battery development is the availability of an electrolyte that can deposit Mg reversibly and at the same time is compatible with a high voltage cathode. We report a prospective full magnesium cell utilizing a simple, non-aqueous electrolyte composed of high concentration magnesium bis(trifluoromethane sulfonyl)imide in diglyme, which is compatible with a high voltage vanadium pentoxide (V 2O 5) cathode and a Mg metal anode. For this system, plating and stripping of Mg metal can be achieved with magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte over a wide concentration range, however, reversible insertion of Mg intomore » V 2O 5 cathode can only be attained at high electrolyte concentrations. Reversible intercalation of Mg into V 2O 5 is characterized and confirmed by X-ray diffraction, X-ray absorption near edge spectroscopy and energy dispersive spectroscopy.« less

Crown Ethers in Nonaqueous Electrolytes for Lithium/Air Batteries

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

Xu, Wu; Xiao, Jie; Wang, Deyu

2010-02-04

The effects of three crown ethers, 12-crown-4, 15-crown-5, and 18-crown-6, as additives and co-solvents in non-aqueous electrolytes on the cell performance of primary Li/air batteries operated in a dry air environment were investigated. Crown ethers have large effects on the discharge performance of non-aqueous electrolytes in Li/air batteries. A small amount (normally less than 10% by weight or volume in electrolytes) of 12-Crown-4 and 15-crown-5 reduces the battery performance and a minimum discharge capacity appears at the crown ether content of ca. 5% in the electrolytes. However, when the content increases to about 15%, both crown ethers improve the capacitymore » of Li/air cells by about 28% and 16%, respectively. 15-Crown-5 based electrolytes even show a maximum discharge capacity in the crown ether content range from 10% to 15%. On the other hand, the increase of 18-crown-6 amount in the electrolytes continuously lowers of the cell performance. The different battery performances of these three crown ethers in electrolytes are explained by the combined effects from the electrolytes’ contact angle, oxygen solubility, viscosity, ionic conductivity, and the stability of complexes formed between crown ether molecules and lithium ions.« less

Non-aqueous electrolyte for high voltage rechargeable magnesium batteries

DOEpatents

Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E; Hwang, Jaehee

2015-02-10

An electrolyte for use in electrochemical cells is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

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

DOEpatents

McCoy, L.R.

1981-01-23

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

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

DOEpatents

McCoy, Lowell R.

1982-01-01

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

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.

Investigation of electrochemical phenomena related to corrosion in high temperature aqueous systems

NASA Astrophysics Data System (ADS)

Biswas, Ritwik

1999-11-01

Three separate phenomena, each related to the problem of corrosion of metals, in high temperature aqueous solutions, have been studied. These are: (1) Kinetics of the Hydrogen Oxidation Reaction (HOR), (2) Effect of solutions containing sulfur oxyanions on Stainless Steel 347 and Inconel 600, and (3) Characterization of electrochemical behavior of intermetallic compounds Ni3Nb and Ni3(TiAl). The anodic transfer coefficient and the Tafel constant, for the HOR, on platinized nickel, in 0.1 m NaOH solution, was experimentally measured over the temperature range of 25°C to 300°C. Potentiodynamic polarization experiments, under controlled hydrodynamic flow conditions, in a cell with annular flow geometry, were used for these measurements. The anodic transfer coefficient and the Tafel constant were found to increase with increase in solution temperature. At high anodic potentials (>1V vs. rest potential), passivation of the platinum electrode was observed. Electron tunneling theory was used to determine that this was the result of formation of platinum oxide (PtO) on the surface of the platinum electrode. The relative corrosion properties of Stainless Steel 347 and Inconel 600, exposed to an aqueous electrolyte containing sulfur oxyanions, at temperatures up to 285°C, was studied using electrochemical tests, mathematical modeling and surface analysis. The presence of sulfur oxyanions was found to cause the breakdown of the protective passive film on both the alloy surfaces, and increase their corrosion rates. As a result of exposure to the electrolyte, a porous layer of corrosion product was formed on both alloys. This porous layer was composed principally of Ni3S2 in the case of Inconel 600 and Fe3O4 in the case of Stainless Steel 347. The corrosive effect of sulfur oxyanions was found to be greater on Inconel 600 than Stainless Steel 347. Galvanic coupling experiments were conducted on the intermetallics Ni 3Nb and Ni3(TiAl) and a nickel rich alloy. It was determined that the intermetallics acted as the anodes when coupled with the nickel rich alloy material. At room temperature, both galvanic current and galvanic potential displayed oscillatory behavior as a function of time. These were analyzed using dynamic systems theory. It was determined from such analysis that the galvanic coupling process can be theoretically described by two coupled ordinary differential equations.

Carbon black dispersion pre-plating technology for printed wire board manufacturing. Final technology evaluation report

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

Folsom, D.W.; Gavaskar, A.R.; Jones, J.A.

1993-10-01

The project compared chemical use, waste generation, cost, and product quality between electroless copper and carbon-black-based preplating technologies at the printed wire board (PWB) manufacturing facility of McCurdy Circuits in Orange, CA. The carbon-black based preplating technology evaluated is used as an alternative process for electroless copper (EC) plating of through-holes before electrolytic copper plating. The specific process used at McCurdy is the BlackHole (BH) technology process, which uses a dispersion of carbon black in an aqueous solution to provide a conductive surface for subsequent electrolytic copper plating. The carbon-black dispersion technology provided effective waste reduction and long-term cost savings.more » The economic analysis determined that the new process was cost efficient because chemical use was reduced and the process proved more efficient; the payback period was less than 4 yrs.« less

Micelle depletion-induced vs. micelle-mediated aggregation in nanoparticles

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

Ray, D., E-mail: debes.phys@gmail.com; Aswal, V. K.

2015-06-24

The phase behavior anionic silica nanoparticle (Ludox LS30) with non-ionic surfactants decaethylene glycol monododecylether (C12E10) and cationic dodecyltrimethyl ammonium bromide (DTAB) in aqueous electrolyte solution has been studied by small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations of nanoparticle (1 wt%), surfactants (1 wt%) and electrolyte (0.1 M NaCl). Each of these nanoparticle–surfactant systems has been examined for different contrast conditions where individual components (nanoparticle or surfactant) are made visible. It is observed that the nanoparticle-micelle system in both the cases lead to the aggregation of nanoparticles. The aggregation is found to be micelle depletion-inducedmore » for C12E10 whereas micelle-mediated aggregation for DTAB. Interestingly, it is also found that phase behavior of mixed surfactant (C12E10 + DTAB) system is similar to that of C12E10 (unlike DTAB) micelles with nanoparticles.« less

Hybrid system for rechargeable magnesium battery with high energy density

PubMed Central

Chang, Zheng; Yang, Yaqiong; Wang, Xiaowei; Li, Minxia; Fu, Zhengwen; Wu, Yuping; Holze, Rudolf

2015-01-01

One of the main challenges of electrical energy storage (EES) is the development of environmentally friendly battery systems with high safety and high energy density. Rechargeable Mg batteries have been long considered as one highly promising system due to the use of low cost and dendrite-free magnesium metal. The bottleneck for traditional Mg batteries is to achieve high energy density since their output voltage is below 2.0 V. Here, we report a magnesium battery using Mg in Grignard reagent-based electrolyte as the negative electrode, a lithium intercalation compound in aqueous solution as the positive electrode, and a solid electrolyte as a separator. Its average discharge voltage is 2.1 V with stable discharge platform and good cycling life. The calculated energy density based on the two electrodes is high. These findings open another door to rechargeable magnesium batteries. PMID:26173624

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries

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

Doris, Sean E.; Ward, Ashleigh L.; Baskin, Artem

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the ratemore » of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm -2 day -1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.« less

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries.

PubMed

Doris, Sean E; Ward, Ashleigh L; Baskin, Artem; Frischmann, Peter D; Gavvalapalli, Nagarjuna; Chénard, Etienne; Sevov, Christo S; Prendergast, David; Moore, Jeffrey S; Helms, Brett A

2017-02-01

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. Here we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm -2  day -1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. This strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries

DOE PAGES

Doris, Sean E.; Ward, Ashleigh L.; Baskin, Artem; ...

2017-01-10

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the ratemore » of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm -2 day -1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.« less

Metal halogen battery system with multiple outlet nozzle for hydrate

DOEpatents

Bjorkman, Jr., Harry K.

1983-06-21

A metal halogen battery system, including at least one cell having a positive electrode and a negative electrode contacted by aqueous electrolyte containing the material of said metal and halogen, store means whereby halogen hydrate is formed and stored as part of an aqueous material, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas formed in the cell to a hydrate former whereby the hydrate is formed in association with the store means, said store means being constructed in the form of a container which includes a filter means, said filter means being inoperative to separate the hydrate formed from the electrolyte, said system having, a hydrate former pump means associated with the store means and being operative to intermix halogen gas with aqueous electrolyte to form halogen hydrate, said hydrate former means including, multiple outlet nozzle means connected with the outlet side of said pump means and being operative to minimize plugging, said nozzle means being comprised of at least one divider means which is generally perpendicular to the rotational axes of gears within the pump means, said divider means acting to divide the flow from the pump means into multiple outlet flow paths.

Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

PubMed

Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

2016-06-13

The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of pressure on the activity coefficients of the solutes and on the solubility of minerals in the system Na-Ca-Cl-SO 4-H 2O to 200°C and 1 kbar and to high NaCl concentration

NASA Astrophysics Data System (ADS)

Monnin, Christophe

1990-12-01

A model is presented which is used to calculate the effect of pressure on activity coefficients of aqueous solutes in the system Na-Ca-Cl-SO 4-H 2O to 200°C. Literature data for the density and compressibility of aqueous binary solutions of Na 2SO 4 and CaCl 2 to 200°C are used to calculate the first and second pressure derivatives of Pitzer's ion interaction model parameters, as well as the standard molal compressibility and volume of these two salts. Empirical correlations between the apparent molal volume and compressibility of the aqueous electrolytes are used to guide the choice of the temperature dependent expressions used for the numerical representation of the derivatives of Pitzer's parameters with respect to pressure. For sodium sulfate solutions, such correlations are used to extrapolate compressibilities to 200°C. The change in the thermodynamic properties of the-CaSO 04 ion pair with pressure is taken into account by the variation of its dissociation constant. The volumetric properties (partial molal volumes and compressibilities) of multicomponent solutions in the Na-Ca-Cl-SO 4-H 2O system can be predicted from the information generated here and the volumetric equations of ROGERS and PITZER (1982) for NaCl. This model is then combined with the high temperature model of MOLLER (1988) of the same system in order to calculate activity coefficients at high pressures to 200°C. The resulting model is validated by comparing calculated and measured solubilities of anhydrite and gypsum in pure water and in NaCl solutions up to 6 M. The agreement between the calculated and measured solubilities of the calcium sulfates is typically better than 10% up to 200°C and 1 kbar. The relevance of temperature and pressure corrections to the activity coefficients of aqueous solutes is discussed in regard to the assumed accuracy with which geochemical models are able to calculate mineral solubilities.

High Energy Density Aqueous Electrochemical Capacitors with a KI-KOH Electrolyte.

PubMed

Wang, Xingfeng; Chandrabose, Raghu S; Chun, Sang-Eun; Zhang, Tianqi; Evanko, Brian; Jian, Zelang; Boettcher, Shannon W; Stucky, Galen D; Ji, Xiulei

2015-09-16

We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

Facile preparation, optical and electrochemical properties of layer-by-layer V2O5 quadrate structures

NASA Astrophysics Data System (ADS)

Zhang, Yifu; Zheng, Jiqi; Wang, Qiushi; Hu, Tao; Tian, Fuping; Meng, Changgong

2017-03-01

Layer-by-layer V2O5 structures self-assembly by quadrate sheets like "multilayer cake" were successfully synthesized using NH4VO3 as the vanadium sources by a facile hydrothermal route and combination of the calcination. The structure and composition were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectrometer, X-ray powder diffraction, Raman and Fourier transform infrared spectroscopy. The optical properties of the as-obtained V2O5 layer-by-layer structures were investigated by the Ultraviolet-visible spectroscopy and photoluminescence spectrum. The electrochemical properties of the as-obtained V2O5 layer-by-layer structures as electrodes in supercapacitor device were measured by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) both in the aqueous and organic electrolyte. The specific capacitance is 347 F g-1 at 1 A g-1 in organic electrolyte, which is improved by 46% compared with 238 F g-1 in aqueous electrolyte. During the cycle performance, the specific capacitances of V2O5 layer-by-layer structures after 100 cycles are 30% and 82% of the initial discharge capacity in the aqueous and organic electrolyte, respectively, indicating the cycle performance is significantly improved in organic electrolyte. Our results turn out that layer-by-layer V2O5 structures are an ideal material for supercapacitor electrode in the present work.

pH-sensitive ion-selective field-effect transistor with zirconium dioxide film

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

Vlasov, Yu.G.; Bratov, A.V.; Tarantov, Yu.A.

1988-09-20

Miniature semiconductor pH sensors for liquid media, i.e., ion-selective field-effect transistors (ISFETs), are silicon field-effect transistors with a two-layer dielectric consisting of a passivating SiO/sub 2/ layer adjoining the silicon and a layer of pH-sensitive material in contact with the electrolyte solution to be tested. This study was devoted to the characteristics of pH-sensitive ISFETs with ZrO/sub 2/ films. The base was p-type silicon (KDB-10) with a (100) surface orientation. A ZrO/sub 2/ layer 10-50 nm thick was applied over the SiO/sub 2/ layer by electron-beam deposition. The measurements were made in aqueous KNO/sub 3/ or KCl solutions.

Investigation of DBS electro-oxidation reaction in the aqueous-organic solution of LiClO4.

PubMed

Darlewski, Witold; Popiel, Stanisław; Nalepa, Tomasz; Gromotowicz, Waldemar; Szewczyk, Rafał; Stankiewicz, Romuald

2010-03-15

A process of dibutyl sulphide (DBS) electro-oxidation using electrolysis and cyclic voltamperometry was investigated in water-methanol solution using different electrodes (platinum, boron doped diamond, graphite and glassy carbon). Obtained results indicate that the DBS electro-oxidation process is irreversible in voltamperometric conditions. It was shown that during DBS electrolytic oxidation on Pt, at the low anode potential (1.8 V), DBS was oxidized to sulphoxide and sulphone. Electrolysis at higher potential (up to 3.0 V) resulted in complete DBS oxidation and formation of various products, including: butyric acid, sulphuric acid, butanesulphinic acid, butanesulphonic acid, identified using gas chromatography (GC-AED) and mass spectrometry (GC-MS) methods. (c) 2009 Elsevier B.V. All rights reserved.

A rationally designed self-standing V2O5 electrode for high voltage non-aqueous all-solid-state symmetric (2.0 V) and asymmetric (2.8 V) supercapacitors.

PubMed

Ghosh, Meena; Vijayakumar, Vidyanand; Soni, Roby; Kurungot, Sreekumar

2018-05-10

The maximum capacitive potential window of certain pseudocapacitive materials cannot be accessed in aqueous electrolytes owing to the low dissociation potential of 1.2 V possessed by water molecules. However, the inferior pseudocapacitance exhibited by the commonly used electrode materials when integrated with non-aqueous electrolytes still remains a challenge in the development of supercapacitors (SC). Proper selection of materials for the electrode and a rational design process are indeed important to overcome these practical intricacies so that such systems can perform well with non-aqueous electrolytes. We address this challenge by fabricating a prototype all-solid-state device designed with high-capacitive V2O5 as the electrode material along with a Li-ion conducting organic electrolyte. V2O5 is synthesized on a pre-treated carbon-fibre paper by adopting an electrochemical deposition technique that effects an improved contact resistance. A judicious electrode preparation strategy makes it possible to overcome the constraints of the low ionic and electrical conductivities imposed by the electrolyte and electrode material, respectively. The device, assembled in a symmetrical fashion, achieves a high specific capacitance of 406 F g-1 (at 1 A g-1). The profitable aspect of using an organic electrolyte is also demonstrated with an asymmetric configuration by using activated carbon as the positive and V2O5 as the negative electrode materials, respectively. The asymmetric device displays a wide working-voltage window of 2.8 V and delivers a high energy density of 102.68 W h kg-1 at a power density of 1.49 kW kg-1. Moreover, the low equivalent series resistance of 9.9 Ω and negligible charge transfer resistance are observed in the impedance spectra, which is a key factor that accounts for such an exemplary performance.

An induced current method for measuring zeta potential of electrolyte solution-air interface.

PubMed

Song, Yongxin; Zhao, Kai; Wang, Junsheng; Wu, Xudong; Pan, Xinxiang; Sun, Yeqing; Li, Dongqing

2014-02-15

This paper reports a novel and very simple method for measuring the zeta potential of electrolyte solution-air interface. When a measuring electrode contacts the electrolyte solution-air interface, an electrical current will be generated due to the potential difference between the electrode-air surface and the electrolyte solution-air interface. The amplitude of the measured electric signal is linearly proportional to this potential difference; and depends only on the zeta potential at the electrolyte solution-air interface, regardless of the types and concentrations of the electrolyte. A correlation between the zeta potential and the measured voltage signal is obtained based on the experimental data. Using this equation, the zeta potential of any electrolyte solution-air interface can be evaluated quickly and easily by inserting an electrode through the electrolyte solution-air interface and measuring the electrical signal amplitude. This method was verified by comparing the obtained results of NaCl, MgCl2 and CaCl2 solutions of different pH values and concentrations with the zeta potential data reported in the published journal papers. Copyright © 2013 Elsevier Inc. All rights reserved.

Rechargeable Ni-Li battery integrated aqueous/nonaqueous system.

PubMed

Li, Huiqiao; Wang, Yonggang; Na, Haitao; Liu, Haimei; Zhou, Haoshen

2009-10-28

A rechargeable Ni-Li battery, in which nickel hydroxide serving as a cathode in an aqueous electrolyte and Li metal serving as an anode in an organic electrolyte were integrated by a superionic conductor glass ceramic film (LISICON), was proposed with the expectation to combine the advantages of both a Li-ion battery and Ni-MH battery. It has the potential for an ultrahigh theoretical energy density of 935 Wh/kg, twice that of a Li-ion battery (414 Wh/kg), based on the active material in electrodes. A prototype Ni-Li battery fabricated in the present work demonstrated a cell voltage of 3.47 V and a capacity of 264 mAh/g with good retention during 50 cycles of charge/discharge. This battery system with a hybrid electrolyte provides a new avenue for the best combination of electrode/electrolyte/electrode to fulfill the potential of high energy density as well as high power density.

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.

Preparation of electrochromic thin films by transformation of manganese(II) carbonate

NASA Astrophysics Data System (ADS)

Stojkovikj, Sasho; Najdoski, Metodija; Koleva, Violeta; Demiri, Sani

2013-10-01

A new chemical bath method for deposition of manganese(II) carbonate thin film on electroconductive FTO glass substrates is designed. The homogeneous thin films with thickness in the range of 70 to 500 nm are deposited at about 98 °C from aqueous solution containing urea and MnCl2. The chemical process is based on a low temperature hydrolysis of the manganese complexes with urea. Three types of films are under consideration: as-deposited, annealed and electrochemically transformed thin films. The structure of the films is studied by XRD, IR and Raman spectroscopy. Electrochemical and optical properties are examined in eight different electrolytes (neutral and alkaline) and the best results are achieved in two component aqueous solution of 0.1 M KNO3 and 0.01 M KOH. It is established that the as-deposited MnCO3 film undergoes electrochemically transformation into birnessite-type manganese(IV) oxide films, which exhibit electrochromic color changes (from bright brown to pale yellow and vice versa) with 30% difference in the transmittance of the colored and bleached state at 400 nm.

Doping and controllable pore size enhanced electrochemical performance of free-standing 3D graphene films

NASA Astrophysics Data System (ADS)

Wang, Liping; Qin, Kaiqiang; Li, Jiajun; Zhao, Naiqin; Shi, Chunsheng; Ma, Liying; He, Chunnian; He, Fang; Liu, Enzuo

2018-01-01

High quality free-standing 3D nanoporous graphene (3DNG) films were fabricated using nanoporous nickel as template and catalyst. The effect of heteroatom doping and pore size on the electrochemical performance of the 3D graphene films as supercapacitor electrodes are systematically studied. Compared with macroporous graphene films, nanoporous graphene films exhibit an extraordinarily large operational window in neutral, acidic and alkaline aqueous electrolytes, as well as high packing density. Nitrogen and oxygen doping play different roles in different aqueous electrolytes on the electrical conductivity and pseudocapacitance of 3DNG. The realization of both high packing density, 3.65 mg/cm2, and the maximum working window, as well as the synergistic effect between N and O doping, gives rise to a high areal capacitance of 435 mF/cm2 in neutral electrolyte and excellent cycle stability up to 5000 cycles. The results provide a potential strategy to further increase the volumetric or areal energy density of carbon-based aqueous supercapacitor.

Highly Conductive Aromatic Functionalized Multi-Walled Carbon Nanotube for Inkjet Printable High Performance Supercapacitor Electrodes

PubMed Central

Attri, Pankaj

2015-01-01

We report the functionalization of multiwalled carbon nanotubes (MWCNT) via the 1,3-dipolar [3+2] cycloaddition of aromatic azides, which resulted in a detangled CNT as shown by transmission electron microscopy (TEM). Carboxylic moieties (-COOH) on aromatic azide result in highly stable aqueous dispersion (max. conc. ~ 10 mg/mL H2O), making the suitable for inkjet printing. Printed patterns on polyethylene terephthalate (PET) flexible substrate exhibit low sheet resistivity ~65 Ω. cm, which is attributed to enhanced conductivity. Fabricated Supercapacitors (SC) assembled using these printed substrates exhibit good electrochemical performance in organic as well as aqueous electrolytes. High energy and power density (57.8 Wh/kg and 0.85 kW/kg) in 1M H2SO4 aqueous electrolyte demonstrate the excellent performance of the proposed supercapacitor. Capacitive retention varies from ~85–94% with columbic efficiency ~95% after 1000 charge/discharge cycles in different electrolytes, demonstrating the excellent potential of the device for futuristic power applications. PMID:26153688

Open-Gated pH Sensor Fabricated on an Undoped-AlGaN/GaN HEMT Structure

PubMed Central

Abidin, Mastura Shafinaz Zainal; Hashim, Abdul Manaf; Sharifabad, Maneea Eizadi; Rahman, Shaharin Fadzli Abd; Sadoh, Taizoh

2011-01-01

The sensing responses in aqueous solution of an open-gated pH sensor fabricated on an AlGaN/GaN high-electron-mobility-transistor (HEMT) structure are investigated. Under air-exposed ambient conditions, the open-gated undoped AlGaN/GaN HEMT only shows the presence of a linear current region. This seems to show that very low Fermi level pinning by surface states exists in the undoped AlGaN/GaN sample. In aqueous solution, typical current-voltage (I-V) characteristics with reasonably good gate controllability are observed, showing that the potential of the AlGaN surface at the open-gated area is effectively controlled via aqueous solution by the Ag/AgCl gate electrode. The open-gated undoped AlGaN/GaN HEMT structure is capable of distinguishing pH level in aqueous electrolytes and exhibits linear sensitivity, where high sensitivity of 1.9 mA/pH or 3.88 mA/mm/pH at drain-source voltage, VDS = 5 V is obtained. Due to the large leakage current where it increases with the negative gate voltage, Nernstian like sensitivity cannot be determined as commonly reported in the literature. This large leakage current may be caused by the technical factors rather than any characteristics of the devices. Surprisingly, although there are some imperfections in the device preparation and measurement, the fabricated devices work very well in distinguishing the pH levels. Suppression of current leakage by improving the device preparation is likely needed to improve the device performance. The fabricated device is expected to be suitable for pH sensing applications. PMID:22163786

Mesopore- and Macropore-Dominant Nitrogen-Doped Hierarchically Porous Carbons for High-Energy and Ultrafast Supercapacitors in Non-Aqueous Electrolytes.

PubMed

Shao, Rong; Niu, Jin; Liang, Jingjing; Liu, Mengyue; Zhang, Zhengping; Dou, Meiling; Huang, Yaqin; Wang, Feng

2017-12-13

Non-aqueous electrolytes (e.g., organic and ionic liquid electrolytes) can undergo high working voltage to improve the energy densities of supercapacitors. However, the large ion sizes, high viscosities, and low ionic conductivities of organic and ionic liquid electrolytes tend to cause the low specific capacitances, poor rate, and cycling performance of supercapacitors based on conventional micropore-dominant activated carbon electrodes, limiting their practical applications. Herein, we propose an effective strategy to simultaneously obtain high power and energy densities in non-aqueous electrolytes via using a cattle bone-derived porous carbon as an electrode material. Because of the unique co-activation of KOH and hydroxyapatite (HA) within the cattle bone, nitrogen-doped hierarchically porous carbon (referred to as NHPC-HA/KOH) is obtained and possesses a mesopore- and macropore-dominant porosity with an ultrahigh specific surface area (2203 m 2 g -1 ) of meso- and macropores. The NHPC-HA/KOH electrodes exhibit superior performance with specific capacitances of 224 and 240 F g -1 at 5 A g -1 in 1.0 M TEABF 4 /AN and neat EMIMBF 4 electrolyte, respectively. The symmetric supercapacitor using NHPC-HA/KOH electrodes can deliver integrated high energy and power properties (48.6 W h kg -1 at 3.13 kW kg -1 in 1.0 M TEABF 4 /AN and 75 W h kg -1 at 3.75 kW kg -1 in neat EMIMBF 4 ), as well as superior cycling performance (over 89% of the initial capacitance after 10 000 cycles at 10 A g -1 ).

Influence of electrical double-layer interaction on coal flotation.

PubMed

Harvey, Paul A; Nguyen, Anh V; Evans, Geoffrey M

2002-06-15

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.

Cloud Point and Liquid-Liquid Equilibrium Behavior of Thermosensitive Polymer L61 and Salt Aqueous Two-Phase System.

PubMed

Rao, Wenwei; Wang, Yun; Han, Juan; Wang, Lei; Chen, Tong; Liu, Yan; Ni, Liang

2015-06-25

The cloud point of thermosensitive triblock polymer L61, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), was determined in the presence of various electrolytes (K2HPO4, (NH4)3C6H5O7, and K3C6H5O7). The cloud point of L61 was lowered by the addition of electrolytes, and the cloud point of L61 decreased linearly with increasing electrolyte concentration. The efficacy of electrolytes on reducing cloud point followed the order: K3C6H5O7 > (NH4)3C6H5O7 > K2HPO4. With the increase in salt concentration, aqueous two-phase systems exhibited a phase inversion. In addition, increasing the temperature reduced the concentration of salt needed that could promote phase inversion. The phase diagrams and liquid-liquid equilibrium data of the L61-K2HPO4/(NH4)3C6H5O7/K3C6H5O7 aqueous two-phase systems (before the phase inversion but also after phase inversion) were determined at T = (25, 30, and 35) °C. Phase diagrams of aqueous two-phase systems were fitted to a four-parameter empirical nonlinear expression. Moreover, the slopes of the tie-lines and the area of two-phase region in the diagram have a tendency to rise with increasing temperature. The capacity of different salts to induce aqueous two-phase system formation was the same order as the ability of salts to reduce the cloud point.

Studies of metals electroprocessing in molten salts

NASA Technical Reports Server (NTRS)

Sadoway, D. R.

1982-01-01

Fluid flow patterns in molten salt electrolytes were observed in order to determine how mass transport affects the morphology of the metal deposit. Studies conducted on the same metal, both in aqueous electrolytes in which coherent solid electrodeposits are produced, as well as in transparent molten salt electrolytes are described. Process variables such as current density and composition of the electrolyte are adjusted to change the morphology of the electrodeposit and, thus, to permit the study of the nature of electrolyte flow in relation to the quality of the electrodeposit.

Study on lithium/air secondary batteries-Stability of NASICON-type lithium ion conducting glass-ceramics with water

NASA Astrophysics Data System (ADS)

Hasegawa, Satoshi; Imanishi, Nobuyuki; Zhang, Tao; Xie, Jian; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu

The water stability of the fast lithium ion conducting glass-ceramic electrolyte, Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATP), has been examined in distilled water, and aqueous solutions of LiNO 3, LiCl, LiOH, and HCl. This glass-ceramics are stable in aqueous LiNO 3 and aqueous LiCl, and unstable in aqueous 0.1 M HCl and 1 M LiOH. In distilled water, the electrical conductivity slightly increases as a function of immersion time in water. The Li-Al/Li 3- xPO 4- yN y/LATP/aqueous 1 M LiCl/Pt cell, where lithium phosphors oxynitrides Li 3- xPO 4- yN y (LiPON) are used to protect the direct reaction of Li and LATP, shows a stable open circuit voltage (OCV) of 3.64 V at 25 °C, and no cell resistance change for 1 week. Lithium phosphors oxynitride is effectively used as a protective layer to suppress the reaction between the LATP and Li metal. The water-stable Li/LiPON/LATP system can be used in Li/air secondary batteries with the air electrode containing water.

Heteroatom incorporated coke for electrochemical cell electrode

DOEpatents

Lewis, Irwin Charles; Greinke, Ronald Alfred

1997-01-01

This invention relates to an electrode for a coke/alkali metal electrochemical cell comprising: (a) calcined coke particles: (i) that contain at least 0.5 weight percent of nitrogen heteroatoms and at least 1.0 weight percent sulfur heteroatoms, and (ii) that have an average particle size from 2 microns to 40 microns with essentially no particles being greater than 50 microns. (b) a binder This invention also relates to a coke/alkali metal electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrically conductive salt, and (c) a counterelectrode.

Chemically modified graphite for electrochemical cells

DOEpatents

Greinke, R.A.; Lewis, I.C.

1998-05-26

This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (1) the electrode, (2) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (3) a counter electrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes. 3 figs.

Chemically modified graphite for electrochemical cells

DOEpatents

Greinke, Ronald Alfred; Lewis, Irwin Charles

1998-01-01

This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (i) the electrode, (ii) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (iii) a counterelectrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes.

Titania nanotube powders obtained by rapid breakdown anodization in perchloric acid electrolytes

NASA Astrophysics Data System (ADS)

Ali, Saima; Hannula, Simo-Pekka

2017-05-01

Titania nanotube (TNT) powders are prepared by rapid break down anodization (RBA) in a 0.1 M perchloric acid (HClO4) solution (Process 1), and ethylene glycol (EG) mixture with HClO4 and water (Process 2). A study of the as-prepared and calcined TNT powders obtained by both processes is implemented to evaluate and compare the morphology, crystal structure, specific surface area, and the composition of the nanotubes. Longer TNTs are formed in Process 1, while comparatively larger pore diameter and wall thickness are obtained for the nanotubes prepared by Process 2. The TNTs obtained by Process 1 are converted to nanorods at 350 °C, while nanotubes obtained by Process 2 preserve tubular morphology till 350 °C. In addition, the TNTs prepared by an aqueous electrolyte have a crystalline structure, whereas the TNTs obtained by Process 2 are amorphous. Samples calcined till 450 °C have XRD peaks from the anatase phase, while the rutile phase appears at 550 °C for the TNTs prepared by both processes. The Raman spectra also show clear anatase peaks for all samples except the as-prepared sample obtained by Process 2, thus supporting the XRD findings. FTIR spectra reveal the presence of O-H groups in the structure for the TNTs obtained by both processes. However, the presence is less prominent for annealed samples. Additionally, TNTs obtained by Process 2 have a carbonaceous impurity present in the structure attributed to the electrolyte used in that process. While a negligible weight loss is typical for TNTs prepared from aqueous electrolytes, a weight loss of 38.6% in the temperature range of 25-600 °C is found for TNTs prepared in EG electrolyte (Process 2). A large specific surface area of 179.2 m2 g-1 is obtained for TNTs prepared by Process 1, whereas Process 2 produces nanotubes with a lower specific surface area. The difference appears to correspond to the dimensions of the nanotubes obtained by the two processes.

Batteries: Widening voltage windows

NASA Astrophysics Data System (ADS)

Xu, Kang; Wang, Chunsheng

2016-10-01

The energy output of aqueous batteries is largely limited by the narrow voltage window of their electrolytes. Now, a hydrate melt consisting of lithium salts is shown to expand such voltage windows, leading to a high-energy aqueous battery.

In-vivo study for anti-hyperglycemic potential of aqueous extract of Basil seeds (Ocimum basilicum Linn) and its influence on biochemical parameters, serum electrolytes and haematological indices.

PubMed

Chaudhary, Sachin; Semwal, Amit; Kumar, Hitesh; Verma, Harish Chandra; Kumar, Amit

2016-12-01

The study introduced anti-hyperglycemic influence of aqueous extract of Ocimum basilicum seeds (AEOBS) in Streptozotocin (STZ) induced diabetic rats and estimating its potential to ameliorate altered level of biochemical parameters, serum electrolytes level and haematological indices along with its effect on body weight of treated rats. The albino rats were selected to observe oral glucose tolerance test by oral intake of aq. glucose solution (4g/kg, body weight) in normal rats and estimation of blood glucose level after administration of AEOBS at 250mg/kg, 500mg/kg and standard drug glibenclamide at 0.6mg/kg, body weight. Antidiabetic activity was evaluated in chronic study models by STZ induced diabetes in rats followed by blood glucose estimation. Chronic study model was selected to carry out further studies to evaluate the effect of AEOBS at 250mg/kg, 500mg/kg and standard drug on body weight, alterations in biochemical parameters including AST, ALT, ALP, total bilirubin and total protein, alterations in serum electrolytes like Na + , K + , Cl - , HCO 3 - along with estimation of haematological indices like red blood cells (RBC), white blood cells (WBC), hemoglobin (Hb), lymphocytes, neutrophils, eosinophils, monocytes and basophils. AEOBS significantly reduced the blood glucose level of diabetic rats at both doses. Body weight was also improved significantly. Similarly, the levels of biochemical parameters, serum electrolytes, and haematological indices were significantly ameliorated at both doses of AEOBS. The histopathological results revealed reconstitution of pancreatic islets towards normal cellular architecture in rats treated with AEOBS. The results illustrated that AEOBS have eminent antidiabetic potential in STZ effectuated diabetes in rats and can be extensively used for the treatment of diabetes mellitus-II and its associated complications including anaemia, diabetic nephropathy, liver dysfunction, and immunosuppression. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Background electrolytes and pH effects on selenate adsorption using iron-impregnated granular activated carbon and surface binding mechanisms.

PubMed

Zhang, Ning; Gang, Daniel Dianchen; McDonald, Louis; Lin, Lian-Shin

2018-03-01

Iron-impregnated granular activated carbon (Fe-GAC) has been shown effective for selenite adsorptive removal from aqueous solutions, but similar effectiveness was not observed with selenate. This study examined the effects of background electrolytes and pH on selenate adsorption on to Fe-GAC, and surface bindings to elucidate the selenate adsorption mechanisms. The decrease magnitude of selenate adsorption capacity under three background electrolytes followed the order: LiCl > NaCl > KCl, as ionic strength increased from 0.01 to 0.1 M. Larger adsorption capacity differences among the three electrolytes were observed under the higher ionic strengths (0.05 and 0.1 M) than those under 0.01 M. Multiplet peak fittings of high resolution X-ray photoelectron spectra for O1s and Fe2p 3/2 indicated the presence of iron (III) on adsorbent surface. pH variations during the adsorbent preparation within 3-8 in NaCl solutions did not cause appreciable changes in the iron redox state and composition. Raman spectra showed the formation of both monodentate and bidentate inner sphere complexes under pHs <7 and a mixture of outer sphere and inner sphere complexes at pH 8. These results explained the lower selenate adsorption under alkaline conditions. Mechanisms for monodentate and bidentate formations and a stable six-member ring structure were proposed. Two strategies were recommended for modifying Fe-GAC preparation procedure to enhance the selenate adsorption: (1) mixed-metal oxide coatings to increase the point of zero charge (pH zpc ); and (2) ferrous iron coating to initially reduce selenate followed by selenite adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

A novel rechargeable zinc-air battery with molten salt electrolyte

NASA Astrophysics Data System (ADS)

Liu, Shuzhi; Han, Wei; Cui, Baochen; Liu, Xianjun; Zhao, Fulin; Stuart, Jessica; Licht, Stuart

2017-02-01

Zinc-air batteries have been proposed for EV applications and large-scale electricity storage such as wind and solar power. Although zinc-air batteries are very promising, there are numerous technological barriers to overcome. We demonstrate for the first time, a new rechargeable zinc-air battery that utilizes a molten Li0.87Na0.63K0.50CO3 eutectic electrolyte with added NaOH. Cyclic voltammetry reveals that a reversible deposition/dissolution of zinc occurs in the molten Li0.87Na0.63K0.50CO3 eutectic. At 550 °C, this zinc-air battery performs with a coulombic efficiency of 96.9% over 110 cycles, having an average charging potential of ∼1.43 V and discharge potential of ∼1.04 V. The zinc-air battery uses cost effective steel and nickel electrodes without the need for any precious metal catalysts. Moreover, the molten salt electrolyte offers advantages over aqueous electrolytes, avoiding the common aqueous alkaline electrolyte issues of hydrogen evolution, Zn dendrite formation, "drying out", and carbonate precipitation.

Boosting the Energy Density of Carbon-Based Aqueous Supercapacitors by Optimizing the Surface Charge.

PubMed

Yu, Minghao; Lin, Dun; Feng, Haobin; Zeng, Yinxiang; Tong, Yexiang; Lu, Xihong

2017-05-08

The voltage of carbon-based aqueous supercapacitors is limited by the water splitting reaction occurring in one electrode, generally resulting in the promising but unused potential range of the other electrode. Exploiting this unused potential range provides the possibility for further boosting their energy density. An efficient surface charge control strategy was developed to remarkably enhance the energy density of multiscale porous carbon (MSPC) based aqueous symmetric supercapacitors (SSCs) by controllably tuning the operating potential range of MSPC electrodes. The operating voltage of the SSCs with neutral electrolyte was significantly expanded from 1.4 V to 1.8 V after simple adjustment, enabling the energy density of the optimized SSCs reached twice as much as the original. Such a facile strategy was also demonstrated for the aqueous SSCs with acidic and alkaline electrolytes, and is believed to bring insight in the design of aqueous supercapacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

MOBI: Microgravity Observations of Bubble Interactions

NASA Technical Reports Server (NTRS)

Koch, Donald L.; Sangani, Ashok

2004-01-01

One of the greatest uncertainties affecting the design of multiphase flow technologies for space exploration is the spatial distribution of phases that will arise in microgravity or reduced gravity. On Earth, buoyancy-driven motion predominates whereas the shearing of the bubble suspension controls its behavior in microgravity. We are conducting a series of ground-based experiments and a flight experiment spanning the full range of ratios of buoyancy to shear. These include: (1) bubbles rising in a quiescent liquid in a vertical channel; (2) weak shear flow induced by slightly inclining the channel; (3) moderate shear flow in a terrestrial vertical pipe flow; and (4) shearing of a bubble suspension in a cylindrical Couette cell in microgravity. We consider nearly monodisperse suspensions of 1 to 1.8 mm diameter bubbles in aqueous electrolyte solutions. The liquid velocity disturbance produced by bubbles in this size range can often be described using an inviscid analysis. Electrolytic solutions lead to hydrophilic repulsion forces that stabilize the bubble suspension without causing Marangoni stresses. We will discuss the mechanisms that control the flow behavior and phase distribution in the ground-based experiments and speculate on the factors that may influence the suspension flow and bubble volume fraction distribution in the flight experiment.

A high-temperature high-pressure calorimeter for determining heats of solution up to 623 K.

PubMed

Djamali, Essmaiil; Turner, Peter J; Murray, Richard C; Cobble, James W

2010-07-01

A high-temperature high-pressure isoperibol calorimeter for determining the heats of solution and reaction of very dilute substances in water (10(-4) m) at temperatures up to 623 K is described. The energies of vaporization of water at steam saturation pressure were measured as a function of temperature and the results agree with the corresponding values from steam tables to better than 0.08+/-0.18%. The novelties of the present instrument relative to flow type heat capacity calorimeters are that measurements can be made at orders of magnitude lower concentrations and that measurement of heat of reaction involving solids or gases or in the presence of high concentrations of supporting electrolytes, acids, and bases is possible. Furthermore, the advantage of using enthalpy data over heat capacity data for calculations of the standard state Gibbs free energies of electrolytes is that the experimental heat data of this research need only be integrated once to derive higher temperature free energy data from lower temperatures. The derived heat capacities can be used mathematically to obtain free energies by double integration. However, the resulting errors are much smaller than if experimental aqueous heat capacities were used for the integrations.

Theoretical analysis of aqueous solutions of mixed strong electrolytes by a smaller-ion shell electrostatic model

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

Fraenkel, Dan, E-mail: dfraenkel@eltronresearch.com

2014-02-07

In spite of the great importance of mixed electrolytes in science and technology, no compelling theoretical explanation has been offered yet for the thermodynamic behavior of such systems, such as their deviation from ideality and the variation of their excess functions with ionic composition and concentration. Using the newly introduced Smaller-ion Shell treatment – an extension of the Debye–Hückel theory to ions of dissimilar size (hence DH–SiS) – simple analytic mathematical expressions can be derived for the mean and single-ion activity coefficients of binary electrolyte components of ternary ionic systems. Such expressions are based on modifying the parallel DH–SiS equationsmore » for pure binary ionic systems, by adding to the three ion-size parameters – a (of counterions), b{sub +} (of positive coions), and b{sub −} (of negative coions) – a fourth parameter. For the (+ + −) system, this is “b{sub ++},” the contact distance between non-coion cations. b{sub ++} is derived from fits with experiment and, like the other b’s, is constant at varying ion concentration and combination. Four case studies are presented: (1) HCl–NaCl–H{sub 2}O, (2) HCl–NH{sub 4}Cl–H{sub 2}O, (3) (0.01 M HX)–MX–H{sub 2}O with X = Cl, Br, and with M = Li, Na, K, Cs, and (4) HCl–MCl{sub n}–H{sub 2}O with n = 2, M = Sr, Ba; and n = 3, M = Al, Ce. In all cases, theory is fully consistent with experiment when using a of the measured binary electrolyte as the sole fitting parameter. DH–SiS is thus shown to explain known “mysteries” in the behavior of ternary electrolytes, including Harned rule, and to adequately predict the pH of acid solutions in which ionized salts are present at different concentrations.« less

Lysozyme pattern formation in evaporating droplets

NASA Astrophysics Data System (ADS)

Gorr, Heather Meloy

Liquid droplets containing suspended particles deposited on a solid, flat surface generally form ring-like structures due to the redistribution of solute during evaporation (the "coffee ring effect"). The forms of the deposited patterns depend on complex interactions between solute(s), solvent, and substrate in a rapidly changing, far from equilibrium system. Solute self-organization during evaporation of colloidal sessile droplets has attracted the attention of researchers over the past few decades due to a variety of technological applications. Recently, pattern formation during evaporation of various biofluids has been studied due to potential applications in medical screening and diagnosis. Due to the complexity of 'real' biological fluids and other multicomponent systems, a comprehensive understanding of pattern formation during droplet evaporation of these fluids is lacking. In this PhD dissertation, the morphology of the patterns remaining after evaporation of droplets of a simplified model biological fluid (aqueous lysozyme solutions + NaCl) are examined by atomic force microscopy (AFM) and optical microscopy. Lysozyme is a globular protein found in high concentration, for example, in human tears and saliva. The drop diameters, D, studied range from the micro- to the macro- scale (1 microm -- 2 mm). In this work, the effect of evaporation conditions, solution chemistry, and heat transfer within the droplet on pattern formation is examined. In micro-scale deposits of aqueous lysozyme solutions (1 microm < D < 50 microm), the protein motion and the resulting dried residue morphology are highly influenced by the decreased evaporation time of the drop. The effect of electrolytes on pattern formation is also investigated by adding varying concentrations NaCl to the lysozyme solutions. Finally, a novel pattern recognition program is described and implemented which classifies deposit images by their solution chemistries. The results presented in this PhD dissertation provide insight into the evaporative behavior and pattern formation in droplets of simplified model biological fluids (aqueous lysozyme + NaCl). The patterns that form depend sensitively on the evaporation conditions, characteristic time and length scales, and the physiochemical properties of the solutions. The patterns are unique, dependent on solution chemistry, and may therefore act as a "fingerprint" in identifying fluid properties.

Measuring the state of charge of the electrolyte solution in a vanadium redox flow battery using a four-pole cell device

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-12-01

The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.

Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

2014-11-01

In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

Thermodynamic Studies of Levitated Microdroplets of Highly Supersaturated Electrolyte Solutions

NASA Technical Reports Server (NTRS)

Myerson, Allan S.; Izmailov, Alexander F.; Na, Han-Soo

1996-01-01

Highly supersaturated electrolyte solutions are studied by employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. A correspondence of 96-99% between the theory and experiment for the all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin) and its calculation for various electrolyte solutions at 298 K.

Electrolytic trapping of iodine from process gas streams

DOEpatents

Horner, Donald E.; Mailen, James C.; Posey, Franz A.

1977-01-25

A method for removing molecular, inorganic, and organic forms of iodine from process gas streams comprises the electrolytic oxidation of iodine in the presence of cobalt-III ions. The gas stream is passed through the anode compartment of a partitioned electrolytic cell having a nitric acid anolyte containing a catalytic amount of cobalt to cause the oxidation of effluent iodine species to aqueous soluble species.

Advances of aqueous rechargeable lithium-ion battery: A review

NASA Astrophysics Data System (ADS)

Alias, Nurhaswani; Mohamad, Ahmad Azmin

2015-01-01

The electrochemical characteristic of the aqueous rechargeable lithium-ion battery has been widely investigated in efforts to design a green and safe technology that can provide a highly specific capacity, high efficiency and long life for high power applications such as the smart grid and electric vehicle. It is believed that the advantages of this battery will overcome the limitations of the rechargeable lithium-ion battery with organic electrolytes that comprise safety and create high fabrication cost issues. This review focuses on the opportunities of the aqueous rechargeable lithium-ion battery compared to the conventional rechargeable lithium-ion battery with organic-based electrolytes. Previously reported studies are briefly summarised, together with the presentation of new findings based on the conductivity, morphology, electrochemical performance and cycling stability results. The factors that influence the electrochemical performance, the challenges and potential of the aqueous rechargeable lithium-ion battery are highlighted in order to understand and maintained the excellent battery performance.

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

NASA Astrophysics Data System (ADS)

Vanderdeelen, Jan

2012-06-01

The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO3 types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO3. H2O), the hexahydrate ikaite (CaCO3.6H2O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

PubMed

Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S; Schott, Jacques

2010-08-03

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.

Membrane-based osmotic heat engine with organic solvent for enhanced power generation from low-grade heat.

PubMed

Shaulsky, Evyatar; Boo, Chanhee; Lin, Shihong; Elimelech, Menachem

2015-05-05

We present a hybrid osmotic heat engine (OHE) system that uses draw solutions with an organic solvent for enhanced thermal separation efficiency. The hybrid OHE system produces sustainable energy by combining pressure-retarded osmosis (PRO) as a power generation stage and membrane distillation (MD) utilizing low-grade heat as a separation stage. While previous OHE systems employed aqueous electrolyte draw solutions, using methanol as a solvent is advantageous because methanol is highly volatile and has a lower heat capacity and enthalpy of vaporization than water. Hence, the thermal separation efficiency of a draw solution with methanol would be higher than that of an aqueous draw solution. In this study, we evaluated the performance of LiCl-methanol as a potential draw solution for a PRO-MD hybrid OHE system. The membrane transport properties as well as performance with LiCl-methanol draw solution were evaluated using thin-film composite (TFC) PRO membranes and compared to the results obtained with a LiCl-water draw solution. Experimental PRO methanol flux and maximum projected power density of 47.1 L m(-2) h(-1) and 72.1 W m(-2), respectively, were achieved with a 3 M LiCl-methanol draw solution. The overall efficiency of the hybrid OHE system was modeled by coupling the mass and energy flows between the thermal separation (MD) and power generation (PRO) stages under conditions with and without heat recovery. The modeling results demonstrate higher OHE energy efficiency with the LiCl-methanol draw solution compared to that with the LiCl-water draw solution under practical operating conditions (i.e., heat recovery<90%). We discuss the implications of the results for converting low-grade heat to power.

Membrane-Based Osmotic Heat Engine with Organic Solvent for Enhanced Power Generation from Low-Grade Heat

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

Shaulsky, E; Boo, C; Lin, SH

We present a hybrid osmotic heat engine (OHE) system that uses draw solutions with an organic solvent for enhanced thermal separation efficiency. The hybrid OHE system produces sustainable energy by combining pressure-retarded osmosis (PRO) as a power generation stage and membrane distillation (MD) utilizing low-grade heat as a separation stage. While previous OHE systems employed aqueous electrolyte draw solutions, using methanol as a solvent is advantageous because methanol is highly volatile and has a lower heat capacity and enthalpy of vaporization than water. Hence, the thermal separation efficiency of a draw solution with methanol would be higher than that ofmore » an aqueous draw solution. In this study, we evaluated the performance of LiCl-methanol as a potential draw solution for a PRO-MD hybrid OHE system. The membrane transport properties as well as performance with LiCl methanol draw solution were evaluated using thin-film composite (TFC) PRO membranes and compared to the results obtained with a LiCl water draw solution. Experimental PRO methanol flux and maximum projected power density of 47.1 L m(-2) h(-1) and 72.1 W m(-2), respectively, were achieved with a 3 M LiCl-methanol draw solution. The overall efficiency of the hybrid OHE system was modeled by coupling the mass and energy flows between the thermal separation (MD) and power generation (PRO) stages under conditions with and without heat recovery. The modeling results demonstrate higher ORE energy efficiency with the LiCl methanol draw solution compared to that with the LiCl water draw solution under practical operating conditions (i.e., heat recovery <90%). We discuss the implications of the results for converting low-grade heat to power.« less

Magnesium Electrorefining in Non-Aqueous Electrolyte at Room Temperature

NASA Astrophysics Data System (ADS)

Kwon, Kyungjung; Park, Jesik; Kusumah, Priyandi; Dilasari, Bonita; Kim, Hansu; Lee, Churl Kyoung

Magnesium, of which application is often limited by its poor corrosion resistance, is more vulnerable to corrosion with existence of metal impurities such as Fe. Therefore, for the refining and recycling of magnesium, high temperature electrolysis using molten salts has been frequently adopted. In this report, the purification of magnesium scrap by electrolysis at room temperature is investigated with non-aqueous electrolytes. An aprotic solvent of tetrahydrofuran (THF) was used as a solvent of the electrolyte. Magnesium scrap was used as anode materials and ethyl magnesium bromide (EtMgBr) was dissolved in THF for magnesium source. The purified magnesium can be uniformly electrodeposited on copper electrode under potentiostatic conditions. The deposits were confirmed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) analysis.

High Rate Oxygen Reduction in Non-aqueous Electrolytes with the Addition of Perfluorinated Additives

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

Wang, Y.; Yang, X.; Zheng, D.

2011-08-04

The discharge rate capability of Li-air batteries is substantially increased by using perfluorinated compounds as oxygen carriers. The solubility of oxygen in a non-aqueous electrolyte can be significantly increased by the introduction of such compounds, which leads to the increase in the diffusion-limited current of oxygen reduction on the gas diffusion electrode in a Li-air battery. The perfluorinated compound is found to be stable within the electrochemical window of the electrolyte. A powder microelectrode and a rotating disk electrode were used to study the gas diffusion-limited current together with a rotating disk electrode. A 5 mA cm{sup -2} discharge ratemore » is demonstrated in a lab Li-O{sub 2} cell.« less

Influence of various Activated Carbon based Electrode Materials in the Performance of Super Capacitor

NASA Astrophysics Data System (ADS)

Ajay, K. M.; Dinesh, M. N.

2018-02-01

Various activated carbon based electrode materials with different surface areas was prepared on stainless steel based refillable super capacitor model using spin coating. Bio Synthesized Activated Carbon (BSAC), Activated Carbon (AC) and Graphite powder are chosen as electrode materials in this paper. Electrode materials prepared using binder solution which is 6% by wt. polyvinylidene difluoride, 94% by wt. dimethyl fluoride. 3M concentrated KOH solution is used as aqueous electrolyte with PVDF thin film as separator. It is tested for electrochemical characterizations and material characterizations. It is observed that the Specific capacitance of Graphite, Biosynthesized active carbon and Commercially available activated carbon are 16.1F g-1, 53.4F g-1 and 107.6F g-1 respectively at 5mV s-1 scan rate.

Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers

PubMed Central

Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

2016-01-01

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180o. PMID:26846891

Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers.

PubMed

Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

2016-02-05

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180(°).

Heteroaggregation of Silver Nanoparticles with Clay Minerals in Aqueous System

NASA Astrophysics Data System (ADS)

Liu, J.; Burrow, E.; Hwang, Y.; Lenhart, J.

2013-12-01

Nanoparticles are increasingly being used in industrial processes and consumer products that exploit their beneficial properties and improve our daily lives. Nevertheless, they also attract attention when released into natural environment due to their potential for causing adverse effects. The fate and transport of nanoparticles in aqueous systems have been the focus of intense study. However, their interactions with other natural particles have received only limited attention. Clay minerals are ubiquitous in most aquatic systems and their variably charged surfaces can act as deposition sites that can alter the fate and transport of nanoparticles in natural aqueous environments. In this study, we investigated the homoaggregation of silver nanoparticles with different coating layers and their heteroaggregation behavior with clay minerals (illite, kaolinite, montmorillonite) in neutral pH solutions. Silver nanoparticles with a nominal diameter of 80 nm were synthesized with three different surface coating layers: uncoated, citrate-coated and Tween-coated. Illite (IMt-2), kaolinite (KGa-2), and montmorillonite (SWy-2) were purchased from the Clay Mineral Society (Indiana) and pretreated to obtain monocationic (Na-clay) and dicationic (Ca-clay) suspensions before the experiments. The change in hydrodynamic diameter as a function of time was monitored using dynamic light scattering (DLS) measurements in order to evaluate early stage aggregation as a function of electrolyte concentration in both the homo- and heteroaggregation scenarios. A shift in the critical coagulation concentration (CCC) values to lower electrolyte concentrations was observed in binary systems, compared to single silver nanoparticle and clay systems. The results also suggest more rapid aggregation in binary system during the early aggregation stage when compared to the single-particle systems. The behavior of citrate-coated silver nanoparticles was similar to that of the bare particles, while the Tween-coated silver nanoparticles showed high stability in both single and binary systems. There were no significant differences in early stage aggregation kinetics observed inthe Na-clay-nanoparticle or Ca-clay-nanoparticle systems, which suggested that the CCC values of the single Na- or Ca-clay suspensions depend only on the electrolyte concentration, not the original cations on the clay surface. These results provide a basic idea for understanding the heteroaggregation of different silver nanoparticles and clays, which can be utilized in further study of fate and transport of engineered nanoparticles in natural aqueous system.

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V 2+ /V 3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V 2+ /V 3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

DOE workshop: Sedimentary systems, aqueous and organic geochemistry

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

Not Available

1993-07-01

A DOE workshop on sedimentary systems, aqueous and organic geochemistry was held July 15-16, 1993 at Lawrence Berkeley Laboratory. Papers were organized into several sections: Fundamental Properties, containing papers on the thermodynamics of brines, minerals and aqueous electrolyte solutions; Geochemical Transport, covering 3-D imaging of drill core samples, hydrothermal geochemistry, chemical interactions in hydrocarbon reservoirs, fluid flow model application, among others; Rock-Water Interactions, with presentations on stable isotope systematics of fluid/rock interaction, fluid flow and petotectonic evolution, grain boundary transport, sulfur incorporation, tracers in geologic reservoirs, geothermal controls on oil-reservoir evolution, and mineral hydrolysis kinetics; Organic Geochemistry covered new methodsmore » for constraining time of hydrocarbon migration, kinetic models of petroleum formation, mudstones in burial diagenesis, compound-specific carbon isotope analysis of petroleums, stability of natural gas, sulfur in sedimentary organic matter, organic geochemistry of deep ocean sediments, direct speciation of metal by optical spectroscopies; and lastly, Sedimentary Systems, covering sequence stratigraphy, seismic reflectors and diagenetic changes in carbonates, geochemistry and origin of regional dolomites, and evidence of large comet or asteroid impacts at extinction boundaries.« less

A comparative study on the solubility and stability of p-phenylenediamine-based organic redox couples for non-aqueous flow batteries

NASA Astrophysics Data System (ADS)

Kim, Hyun-seung; Lee, Keon-Joon; Han, Young-Kyu; Ryu, Ji Heon; Oh, Seung M.

2017-04-01

A methyl-substituted p-phenylenediamine (PD), N,N,N‧,N‧-tetramethyl-p-phenylenediamine (TMPD), is examined as a positive redox couple with high energy density for non-aqueous Li-flow batteries. Methyl substitution affects the solubility of the redox couple, as the solubility is increased by a factor of ten, to a maximum solubility of 5.0 M in 1.0 M lithium tetrafluoroborate-propylene carbonate supporting electrolyte due to elimination of the hydrogen bonding between the solute molecules. The methyl substitution also enhances the chemical stability of the cation radical and di-cation being generated from PD, as the redox center is shielded by the methyl groups. Furthermore, this organic redox couple demonstrate two-electron redox reactions at 3.2 and 3.8 V (vs. Li/Li+); therefore, the volumetric capacity is twice higher compared to conventional one-electron involved redox couples. In a non-flowing Li/TMPD coin-cell, this organic redox couple demonstrates very stable cycleability as a positive redox couple for non-aqueous flow batteries.

Non-aqueous electrolyte for lithium-ion battery

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

2014-04-15

The present technology relates to stabilizing additives and electrolytes containing the same for use in electrochemical devices such as lithium ion batteries and capacitors. The stabilizing additives include triazinane triones and bicyclic compounds comprising succinic anhydride, such as compounds of Formulas I and II described herein.

Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes.

PubMed

Borodin, Oleg; Suo, Liumin; Gobet, Mallory; Ren, Xiaoming; Wang, Fei; Faraone, Antonio; Peng, Jing; Olguin, Marco; Schroeder, Marshall; Ding, Michael S; Gobrogge, Eric; von Wald Cresce, Arthur; Munoz, Stephen; Dura, Joseph A; Greenbaum, Steve; Wang, Chunsheng; Xu, Kang

2017-10-24

Using molecular dynamics simulations, small-angle neutron scattering, and a variety of spectroscopic techniques, we evaluated the ion solvation and transport behaviors in aqueous electrolytes containing bis(trifluoromethanesulfonyl)imide. We discovered that, at high salt concentrations (from 10 to 21 mol/kg), a disproportion of cation solvation occurs, leading to a liquid structure of heterogeneous domains with a characteristic length scale of 1 to 2 nm. This unusual nano-heterogeneity effectively decouples cations from the Coulombic traps of anions and provides a 3D percolating lithium-water network, via which 40% of the lithium cations are liberated for fast ion transport even in concentration ranges traditionally considered too viscous. Due to such percolation networks, superconcentrated aqueous electrolytes are characterized by a high lithium-transference number (0.73), which is key to supporting an assortment of battery chemistries at high rate. The in-depth understanding of this transport mechanism establishes guiding principles to the tailored design of future superconcentrated electrolyte systems.

Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors.

PubMed

Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa

2017-08-03

The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.

Toward an Aqueous Solar Battery: Direct Electrochemical Storage of Solar Energy in Carbon Nitrides.

PubMed

Podjaski, Filip; Kröger, Julia; Lotsch, Bettina V

2018-03-01

Graphitic carbon nitrides have emerged as an earth-abundant family of polymeric materials for solar energy conversion. Herein, a 2D cyanamide-functionalized polyheptazine imide (NCN-PHI) is reported, which for the first time enables the synergistic coupling of two key functions of energy conversion within one single material: light harvesting and electrical energy storage. Photo-electrochemical measurements in aqueous electrolytes reveal the underlying mechanism of this "solar battery" material: the charge storage in NCN-PHI is based on the photoreduction of the carbon nitride backbone and charge compensation is realized by adsorption of alkali metal ions within the NCN-PHI layers and at the solution interface. The photoreduced carbon nitride can thus be described as a battery anode operating as a pseudocapacitor, which can store light-induced charge in the form of long-lived, "trapped" electrons for hours. Importantly, the potential window of this process is not limited by the water reduction reaction due to the high intrinsic overpotential of carbon nitrides for hydrogen evolution, potentially enabling new applications for aqueous batteries. Thus, the feasibility of light-induced electrical energy storage and release on demand by a one-component light-charged battery anode is demonstrated, which provides a sustainable solution to overcome the intermittency of solar radiation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superior capacitive performance of hydrochar-based porous carbons in aqueous electrolytes.

PubMed

Fuertes, Antonio B; Sevilla, Marta

2015-03-01

Biomass-based highly porous carbons with excellent performances in aqueous electrolyte-based supercapacitors have been developed. The synthesis of these materials is based on the chemical activation of biomass-based hydrochar. The addition of melamine to the activation mixture leads to porous carbons with a porosity consisting of micropores/small mesopores. Furthermore, melamine promotes the introduction of nitrogen heteroatoms in the carbon framework, along with abundant oxygen functionalities, to improve the wettability. The materials produced in the presence or absence of melamine exhibit high specific capacitances in aqueous electrolytes (>270 F g(-1) in H2 SO4 and >190 F g(-1) in Li2SO4). Additionally, the mesopores present in the melamine-based micro-/mesoporous carbons notably improve the ion-transport kinetics, especially in Li2SO4. Furthermore, in Li2SO4, they remain stable up to a cell voltage of 1.6 V; thus exhibiting superior energy and power characteristics than those in H2 SO4. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cost-driven materials selection criteria for redox flow battery electrolytes

NASA Astrophysics Data System (ADS)

Dmello, Rylan; Milshtein, Jarrod D.; Brushett, Fikile R.; Smith, Kyle C.

2016-10-01

Redox flow batteries show promise for grid-scale energy storage applications but are presently too expensive for widespread adoption. Electrolyte material costs constitute a sizeable fraction of the redox flow battery price. As such, this work develops a techno-economic model for redox flow batteries that accounts for redox-active material, salt, and solvent contributions to the electrolyte cost. Benchmark values for electrolyte constituent costs guide identification of design constraints. Nonaqueous battery design is sensitive to all electrolyte component costs, cell voltage, and area-specific resistance. Design challenges for nonaqueous batteries include minimizing salt content and dropping redox-active species concentration requirements. Aqueous battery design is sensitive to only redox-active material cost and cell voltage, due to low area-specific resistance and supporting electrolyte costs. Increasing cell voltage and decreasing redox-active material cost present major materials selection challenges for aqueous batteries. This work minimizes cost-constraining variables by mapping the battery design space with the techno-economic model, through which we highlight pathways towards low price and moderate concentration. Furthermore, the techno-economic model calculates quantitative iterations of battery designs to achieve the Department of Energy battery price target of 100 per kWh and highlights cost cutting strategies to drive battery prices down further.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, Kenneth Orville

1998-01-01

A polymer bonded sheet product suitable for use as an electrode in a non-aqueous battery system. A porous electrode sheet is impregnated with a solid polymer electrolyte, so as to diffuse into the pores of the electrode. The composite is allowed to cool, and the electrolyte is entrapped in the porous electrode. The sheet products composed have the solid polymer electrolyte composition diffused into the active electrode material by melt-application of the solid polymer electrolyte composition into the porous electrode material sheet. The solid polymer electrolyte is maintained at a temperature that allows for rapid diffusion into the pores of the electrode. The composite electrolyte-electrode sheets are formed on current collectors and can be coated with solid polymer electrolyte prior to battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte coating has low resistance.

Function-Space-Based Solution Scheme for the Size-Modified Poisson-Boltzmann Equation in Full-Potential DFT.

PubMed

Ringe, Stefan; Oberhofer, Harald; Hille, Christoph; Matera, Sebastian; Reuter, Karsten

2016-08-09

The size-modified Poisson-Boltzmann (MPB) equation is an efficient implicit solvation model which also captures electrolytic solvent effects. It combines an account of the dielectric solvent response with a mean-field description of solvated finite-sized ions. We present a general solution scheme for the MPB equation based on a fast function-space-oriented Newton method and a Green's function preconditioned iterative linear solver. In contrast to popular multigrid solvers, this approach allows us to fully exploit specialized integration grids and optimized integration schemes. We describe a corresponding numerically efficient implementation for the full-potential density-functional theory (DFT) code FHI-aims. We show that together with an additional Stern layer correction the DFT+MPB approach can describe the mean activity coefficient of a KCl aqueous solution over a wide range of concentrations. The high sensitivity of the calculated activity coefficient on the employed ionic parameters thereby suggests to use extensively tabulated experimental activity coefficients of salt solutions for a systematic parametrization protocol.

A molecular Debye-Hückel theory and its applications to electrolyte solutions: The size asymmetric case

DOE PAGES

Xiao, Tiejun; Song, Xueyu

2017-03-28

We developed a molecular Debye-Hückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of Debye-Hückel-like response modes. Furthermore, as the size asymmetry of an electrolyte solution leads to a charge imbalanced border zone around a solute, the dielectric response to the solute is characterized by two types of charge sources, namely, a bare solute charge and a charge distribution due to size asymmetry. These two kinds of charge sources are screened by the solvent differently, our theory presents a method to calculate the mean electric potential asmore » well as the electrostatic contributions to thermodynamic properties. Finally, the theory was successfully applied to binary as well as multi-component primitive models of electrolyte solutions.« less

High performing solution-coated electrolyte-gated organic field-effect transistors for aqueous media operation.

PubMed

Zhang, Qiaoming; Leonardi, Francesca; Casalini, Stefano; Temiño, Inés; Mas-Torrent, Marta

2016-12-22

Since the first demonstration, the electrolyte-gated organic field-effect transistors (EGOFETs) have immediately gained much attention for the development of cutting-edge technology and they are expected to have a strong impact in the field of (bio-)sensors. However EGOFETs directly expose their active material towards the aqueous media, hence a limited library of organic semiconductors is actually suitable. By using two mostly unexplored strategies in EGOFETs such as blended materials together with a printing technique, we have successfully widened this library. Our benchmarks were 6,13-bis(triisopropylsilylethynyl)pentacene and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), which have been firstly blended with polystyrene and secondly deposited by means of the bar-assisted meniscus shearing (BAMS) technique. Our approach yielded thin films (i.e. no thicker than 30 nm) suitable for organic electronics and stable in liquid environment. Up to date, these EGOFETs show unprecedented performances. Furthermore, an extremely harsh environment, like NaCl 1M, has been used in order to test the limit of operability of these electronic devices. Albeit an electrical worsening is observed, our devices can operate under different electrical stresses within the time frame of hours up to a week. In conclusion, our approach turns out to be a powerful tool for the EGOFET manufacturing.

High performing solution-coated electrolyte-gated organic field-effect transistors for aqueous media operation

NASA Astrophysics Data System (ADS)

Zhang, Qiaoming; Leonardi, Francesca; Casalini, Stefano; Temiño, Inés; Mas-Torrent, Marta

2016-12-01

Since the first demonstration, the electrolyte-gated organic field-effect transistors (EGOFETs) have immediately gained much attention for the development of cutting-edge technology and they are expected to have a strong impact in the field of (bio-)sensors. However EGOFETs directly expose their active material towards the aqueous media, hence a limited library of organic semiconductors is actually suitable. By using two mostly unexplored strategies in EGOFETs such as blended materials together with a printing technique, we have successfully widened this library. Our benchmarks were 6,13-bis(triisopropylsilylethynyl)pentacene and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), which have been firstly blended with polystyrene and secondly deposited by means of the bar-assisted meniscus shearing (BAMS) technique. Our approach yielded thin films (i.e. no thicker than 30 nm) suitable for organic electronics and stable in liquid environment. Up to date, these EGOFETs show unprecedented performances. Furthermore, an extremely harsh environment, like NaCl 1M, has been used in order to test the limit of operability of these electronic devices. Albeit an electrical worsening is observed, our devices can operate under different electrical stresses within the time frame of hours up to a week. In conclusion, our approach turns out to be a powerful tool for the EGOFET manufacturing.

High performing solution-coated electrolyte-gated organic field-effect transistors for aqueous media operation

PubMed Central

Zhang, Qiaoming; Leonardi, Francesca; Casalini, Stefano; Temiño, Inés; Mas-Torrent, Marta

2016-01-01

Since the first demonstration, the electrolyte-gated organic field-effect transistors (EGOFETs) have immediately gained much attention for the development of cutting-edge technology and they are expected to have a strong impact in the field of (bio-)sensors. However EGOFETs directly expose their active material towards the aqueous media, hence a limited library of organic semiconductors is actually suitable. By using two mostly unexplored strategies in EGOFETs such as blended materials together with a printing technique, we have successfully widened this library. Our benchmarks were 6,13-bis(triisopropylsilylethynyl)pentacene and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), which have been firstly blended with polystyrene and secondly deposited by means of the bar-assisted meniscus shearing (BAMS) technique. Our approach yielded thin films (i.e. no thicker than 30 nm) suitable for organic electronics and stable in liquid environment. Up to date, these EGOFETs show unprecedented performances. Furthermore, an extremely harsh environment, like NaCl 1M, has been used in order to test the limit of operability of these electronic devices. Albeit an electrical worsening is observed, our devices can operate under different electrical stresses within the time frame of hours up to a week. In conclusion, our approach turns out to be a powerful tool for the EGOFET manufacturing. PMID:28004824

Thermodynamic Modeling of Organic-Inorganic Aerosols with the Group-Contribution Model AIOMFAC

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, T.

2009-04-01

Liquid aerosol particles are - from a physicochemical viewpoint - mixtures of inorganic salts, acids, water and a large variety of organic compounds (Rogge et al., 1993; Zhang et al., 2007). Molecular interactions between these aerosol components lead to deviations from ideal thermodynamic behavior. Strong non-ideality between organics and dissolved ions may influence the aerosol phases at equilibrium by means of liquid-liquid phase separations into a mainly polar (aqueous) and a less polar (organic) phase. A number of activity models exists to successfully describe the thermodynamic equilibrium of aqueous electrolyte solutions. However, the large number of different, often multi-functional, organic compounds in mixed organic-inorganic particles is a challenging problem for the development of thermodynamic models. The group-contribution concept as introduced in the UNIFAC model by Fredenslund et al. (1975), is a practical method to handle this difficulty and to add a certain predictability for unknown organic substances. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems (Zuend et al., 2008). This model enables the computation of vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semi-empirical middle-range parametrization of direct organic-inorganic interactions in alcohol-water-salt solutions enables accurate computations of vapor-liquid and liquid-liquid equilibria. References Fredenslund, A., Jones, R. L., and Prausnitz, J. M.: Group-Contribution Estimation of Activity Coefficients in Nonideal Liquid Mixtures, AIChE J., 21, 1086-1099, 1975. Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of Urban Organic Aerosols at a Molecular Level: Identification, Abundance and Seasonal Variation, Atmos. Environ., 27, 1309-1330, 1993. Zhang, Q. et al.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13 801, 2007. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.

Chemical potentials of alkaline earth metal halide aqueous electrolytes and solubility of their hydrates by molecular simulation: Application to CaCl2, antarcticite, and sinjarite

NASA Astrophysics Data System (ADS)

Moučka, Filip; Kolafa, Jiří; Lísal, Martin; Smith, William R.

2018-06-01

We present a molecular-level simulation study of CaCl2 in water and crystalline hydrates formed by CaCl2 at ambient (298.15 K, 1 bar) conditions and at a high-temperature high-pressure state (365 K, 275 bars) typical of hydraulic fracturing conditions in natural-gas extraction, at which experimental properties are poorly characterized. We focus on simulations of chemical potentials in both solution and crystalline phases and on the salt solubility, the first time to our knowledge that such properties have been investigated by molecular simulation for divalent aqueous electrolytes. We first extend our osmotic ensemble Monte Carlo simulation technique [F. Moučka et al., J. Phys. Chem. B 115, 7849-7861 (2011)] to such solutions. We then describe and apply new methodology for the simulation of the chemical potentials of the experimentally observed crystalline hydrates at ambient conditions (antarcticite, CaCl2.6H2O) and at high-temperature conditions (sinjarite, CaCl2.2H2O). We implement our methodologies using for both phases the CaCl2 transferable force field (FF) based on simple point charge-extended water developed by Mamatkulov et al. [J. Chem. Phys. 138, 024505 (2013)], based on training sets involving single-ion and ion-pair low-concentration solution properties at near-ambient conditions. We find that simulations of the solution chemical potentials at high concentrations are somewhat problematic, exhibiting densities diverging from experimental values and accompanied by dramatically decreasing particle mobility. For the solid phases, the sinjarite crystalline lattice differs from experiment only slightly, whereas the simulations of antarcticite completely fail, due to instability of the crystalline lattice. The FF thus only successfully yields the sinjarite solubility, but its value m = 8.0(7) mol kg-1H2O lies well below the experimentally observed solubility range at 1 bar pressure of (12m, 15m) in the temperature interval (320 K, 400 K). We conclude that the used FF does not provide a good description of the experimental properties considered and suggest that improvement must take into account the crystalline properties.

Chemical potentials of alkaline earth metal halide aqueous electrolytes and solubility of their hydrates by molecular simulation: Application to CaCl2, antarcticite, and sinjarite.

PubMed

Moučka, Filip; Kolafa, Jiří; Lísal, Martin; Smith, William R

2018-06-14

We present a molecular-level simulation study of CaCl 2 in water and crystalline hydrates formed by CaCl 2 at ambient (298.15 K, 1 bar) conditions and at a high-temperature high-pressure state (365 K, 275 bars) typical of hydraulic fracturing conditions in natural-gas extraction, at which experimental properties are poorly characterized. We focus on simulations of chemical potentials in both solution and crystalline phases and on the salt solubility, the first time to our knowledge that such properties have been investigated by molecular simulation for divalent aqueous electrolytes. We first extend our osmotic ensemble Monte Carlo simulation technique [F. Moučka et al., J. Phys. Chem. B 115, 7849-7861 (2011)] to such solutions. We then describe and apply new methodology for the simulation of the chemical potentials of the experimentally observed crystalline hydrates at ambient conditions (antarcticite, CaCl 2 ·6H 2 O) and at high-temperature conditions (sinjarite, CaCl 2 ·2H 2 O). We implement our methodologies using for both phases the CaCl 2 transferable force field (FF) based on simple point charge-extended water developed by Mamatkulov et al. [J. Chem. Phys. 138, 024505 (2013)], based on training sets involving single-ion and ion-pair low-concentration solution properties at near-ambient conditions. We find that simulations of the solution chemical potentials at high concentrations are somewhat problematic, exhibiting densities diverging from experimental values and accompanied by dramatically decreasing particle mobility. For the solid phases, the sinjarite crystalline lattice differs from experiment only slightly, whereas the simulations of antarcticite completely fail, due to instability of the crystalline lattice. The FF thus only successfully yields the sinjarite solubility, but its value m = 8.0(7) mol kg -1 H 2 O lies well below the experimentally observed solubility range at 1 bar pressure of (12m, 15m) in the temperature interval (320 K, 400 K). We conclude that the used FF does not provide a good description of the experimental properties considered and suggest that improvement must take into account the crystalline properties.

Electrolytic orthoborate salts for lithium batteries

DOEpatents

Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ

2008-01-01

Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.

Electrolytic orthoborate salts for lithium batteries

DOEpatents

Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ

2009-05-05

Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.

High performance methanol-oxygen fuel cell with hollow fiber electrode

NASA Technical Reports Server (NTRS)

Lawson, Daniel D. (Inventor); Ingham, John D. (Inventor)

1983-01-01

A methanol/air-oxygen fuel cell including an electrode formed by open-ended ion-exchange hollow fibers having a layer of catalyst deposited on the inner surface thereof and a first current collector in contact with the catalyst layer. A second current collector external of said fibers is provided which is immersed along with the hollow fiber electrode in an aqueous electrolyte body. Upon passage of air or oxygen through the hollow fiber electrode and introduction of methanol into the aqueous electrolyte, a steady current output is obtained. Two embodiments of the fuel cell are disclosed. In the first embodiment the second metal electrode is displaced away from the hollow fiber in the electrolyte body while in the second embodiment a spiral-wrap electrode is provided about the outer surface of the hollow fiber electrode.

Facile preparation and enhanced capacitance of the polyaniline/sodium alginate nanofiber network for supercapacitors.

PubMed

Li, Yingzhi; Zhao, Xin; Xu, Qian; Zhang, Qinghua; Chen, Dajun

2011-05-17

A porous and mat-like polyaniline/sodium alginate (PANI/SA) composite with excellent electrochemical properties was polymerized in an aqueous solution with sodium sulfate as a template. Ultraviolet-visible spectra, X-ray diffraction pattern, and Fourier transform infrared spectra were employed to characterize the PANI/SA composite, indicating that the PANI/SA composite was successfully prepared. The PANI/SA nanofibers with uniform diameters from 50 to 100 nm can be observed on scanning electron microscopy. Cyclic voltammetry and galvanostatic charge/discharge tests were carried out to investigate the electrochemical properties. The PANI/SA nanostructure electrode exhibits an excellent specific capacitance as high as 2093 F g(-1), long cycle life, and fast reflect of oxidation/reduction on high current changes. The remarkable electrochemical characteristic is attributed to the nanostructured electrode materials, which generates a high electrode/electrolyte contact area and short path lengths for electronic transport and electrolyte ion. The approach is simple and can be easily extended to fabricate nanostructural composites for supercapacitor electrode materials.

High-performance graphene-based supercapacitors made by a scalable blade-coating approach

NASA Astrophysics Data System (ADS)

Wang, Bin; Liu, Jinzhang; Mirri, Francesca; Pasquali, Matteo; Motta, Nunzio; Holmes, John W.

2016-04-01

Graphene oxide (GO) sheets can form liquid crystals (LCs) in their aqueous dispersions that are more viscous with a stronger LC feature. In this work we combine the viscous LC-GO solution with the blade-coating technique to make GO films, for constructing graphene-based supercapacitors in a scalable way. Reduced GO (rGO) films are prepared by wet chemical methods, using either hydrazine (HZ) or hydroiodic acid (HI). Solid-state supercapacitors with rGO films as electrodes and highly conductive carbon nanotube films as current collectors are fabricated and the capacitive properties of different rGO films are compared. It is found that the HZ-rGO film is superior to the HI-rGO film in achieving high capacitance, owing to the 3D structure of graphene sheets in the electrode. Compared to gelled electrolyte, the use of liquid electrolyte (H2SO4) can further increase the capacitance to 265 F per gram (corresponding to 52 mF per cm2) of the HZ-rGO film.

Microwave dielectric study of an oligomeric electrolyte gelator by time domain reflectometry.

PubMed

Kundu, Shyamal Kumar; Yagihara, Shin; Yoshida, Masaru; Shibayama, Mitsuhiro

2009-07-30

The dynamics of water molecules in aqueous solutions of an oligomeric electrolyte gelator, poly[pyridinium-1,4-diyliminocarbonyl-1,4-phenylene-methylene chloride] (1-Cl) was characterized by microwave dielectric measurements using the time domain reflectometry method. The dielectric dispersion and absorption curves related to the orientational motion of water molecules were described by the Cole-Cole equation. Discontinuities were observed in the concentration dependence of the dielectric relaxation strength, Deltaepsilonh, as well as in the Cole-Cole parameter, betah. These discontinuities were observed between the samples with concentrations of 6 and 7 g/L 1-Cl/water, which correspond to a change in the transparency. Such a discontinuity corresponds to the observation of the critical concentration of gelation. The interaction between water and 1-Cl molecules was discussed from the tauh-betah diagram. As 1-Cl carries an amide group, it could be expected that 1-Cl may interact hydrophilically with water, but the present result suggests that 1-Cl interact hydrophobically with water.

A Sinusoidal Applied Electric Potential can Induce a Long-Range, Steady Electrophoretic Force

NASA Astrophysics Data System (ADS)

Amrei, Seyyed Hashemi; Ristenpart, William D.; Miller, Greg R.

2017-11-01

We use the standard electrokinetic model to numerically investigate the electric field in aqueous solutions between parallel electrodes under AC polarization. In contrast to prior work, we invoke no simplifying assumptions regarding the applied voltage, frequency, or mismatch in ionic mobilities. We find that the nonlinear electromigration terms significantly contribute to the overall shape of the electric potential vs. time, which at sufficiently high applied potentials develops multi-modal peaks. More surprisingly, we find that electrolytes with non-equal mobilities yield an electric field with non-zero time average at large distances from the electrodes. Our calculations indicate this long-range electric field suffices to levitate colloidal particles many microns away from the electrode against the gravitational field, in accord with experimental observations of such behavior (Woehl et al., PRX, 2015). Moreover, the results indicate that particles will aggregate laterally near electrodes in some electrolytes but separate in others, helping explain a longstanding but not well understood phenomenon.

Compacted carbon for electrochemical cells

DOEpatents

Greinke, Ronald Alfred; Lewis, Irwin Charles

1997-01-01

This invention provides compacted carbon that is useful in the electrode of an alkali metal/carbon electrochemical cell of improved capacity selected from the group consisting of: (a) coke having the following properties: (i) an x-ray density of at least 2.00 grams per cubic centimeters, (ii) a closed porosity of no greater than 5%, and (iii) an open porosity of no greater than 47%; and (b) graphite having the following properties: (i) an x-ray density of at least 2.20 grams per cubic centimeters, (ii) a closed porosity of no greater than 5%, and (iii) an open porosity of no greater than 25%. This invention also relates to an electrode for an alkali metal/carbon electrochemical cell comprising compacted carbon as described above and a binder. This invention further provides an alkali metal/carbon electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrolytically conductive salt and an alkali metal, and (c) a counterelectrode.

Compacted carbon for electrochemical cells

DOEpatents

Greinke, R.A.; Lewis, I.C.

1997-10-14

This invention provides compacted carbon that is useful in the electrode of an alkali metal/carbon electrochemical cell of improved capacity selected from the group consisting of: (a) coke having the following properties: (1) an x-ray density of at least 2.00 grams per cubic centimeters, (2) a closed porosity of no greater than 5%, and (3) an open porosity of no greater than 47%; and (b) graphite having the following properties: (1) an x-ray density of at least 2.20 grams per cubic centimeters, (2) a closed porosity of no greater than 5%, and (3) an open porosity of no greater than 25%. This invention also relates to an electrode for an alkali metal/carbon electrochemical cell comprising compacted carbon as described above and a binder. This invention further provides an alkali metal/carbon electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrolytically conductive salt and an alkali metal, and (c) a counter electrode. 10 figs.

Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

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

Ji, Jianlong; Li, Pengwei; Sang, Shengbo, E-mail: sbsang@tyut.edu.cn

2014-03-15

Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electricmore » field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.« less

Photointercalating Semiconductor/Solid Electrolyte Junctions for Storage and Chemical Detection. Phase 2.

DTIC Science & Technology

1988-05-31

character- isti, s of single crystal n-HfS 2 in liquid non-aqueous electrolyte (acetonitrile containing O.1M tetrabutylammonium hexafluorophosphate ...INC There are several incentives for the direct detection of SO2 under ambient conditions. These include potential leakage from pressurized lithium /SO

[Evaluation of the Peusner's coefficients matrix for polymeric membrane and ternary non-electrolyte solutions].

PubMed

Jasik-Slęzak, Jolanta; Slęzak-Prochazka, Izabella; Slęzak, Andrzej

2014-01-01

A system of network forms of Kedem-Katchalsky (K-K) equations for ternary non-electrolyte solutions is made of eight matrix equations containing Peusner's coefficients R(ij), L(ij), H(ij), W(ij), K(ij), N(ij), S(ij) or P(ij) (i, j ∈ {1, 2, 3}). The equations are the result of symmetric or hybrid transformation of the classic form of K-K equations by the use of methods of Peusner's network thermodynamics (PNT). Calculating concentration dependences of the determinant of Peusner's coefficients matrixes R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) and P(ij) (i, j ∈ {1, 2, 3}). The material used in the experiment was a hemodialysis Nephrophan membrane with specified transport properties (L(p), σ, Ω) in aqueous glucose and ethanol solution. The method involved equations for determinants of the matrixes coefficients R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) or P(ij) (i, j ∈ {1, 2, 3}). The objective of calculations were dependences of determinants of Peusner's coeffcients matrixes R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) or P(ij) (i, j ∈ {1, 2, 3}) within the conditions of solution homogeneity upon an average concentration of one component of solution in the membrane (C1) with a determined value of the second component (C2). The method of calculating the determinants of Peusner's coeffcients matrixes R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) or P(ij) (i, j ∈ {1, 2, 3}) is a new tool that may be applicable in studies on membrane transport. Calculations showed that the coefficients are sensitive to concentration and composition of solutions separated by a polymeric membrane.

Heteroatom incorporated coke for electrochemical cell electrode

DOEpatents

Lewis, I.C.; Greinke, R.A.

1997-06-17

This invention relates to an electrode for a coke/alkali metal electrochemical cell comprising: (a) calcined coke particles: (1) that contain at least 0.5 weight percent of nitrogen heteroatoms and at least 1.0 weight percent sulfur heteroatoms, and (2) that have an average particle size from 2 microns to 40 microns with essentially no particles being greater than 50 microns and (b) a binder. This invention also relates to a coke/alkali metal electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrically conductive salt, and (c) a counterelectrode. 5 figs.

Zn/gelled 6 M KOH/O 2 zinc-air battery

NASA Astrophysics Data System (ADS)

Mohamad, A. A.

The gel electrolyte for the zinc-air cell was prepared by mixing hydroponics gel with a 6 M potassium hydroxide aqueous solution. The self-discharge of cells was characterized by measuring the open-circuit voltage. The effect of a discharge rate of 50 mA constant current on cell voltage and plateau hour, as well as the voltage-current and current density-power density were measured and analysed. The electrode degradation after discharge cycling was characterized by structural and surface methods. The oxidation of the electrode surface further blocked the utilization of the Zn anode and was identified as a cause for the failure of the cell.

Electrical characterization of TiO2 nanotubes synthesized through electrochemical anodizing method

NASA Astrophysics Data System (ADS)

Manescu Paltanea, Veronica; Paltanea, Gheorghe; Popovici, Dorina; Jiga, Gabriel

2016-05-01

In the present paper, the electrochemical anodizing method was used for the obtaining of TiO2 nanotube layers, developed on titanium surface. Self-organized titanium nanotubes were obtained when an aqueous solution of 49.5 wt % H2O - 49.5 wt % glycerol - 1 wt % HF was used as electrolyte, the anodizing time being equal to 8 hours and the applied voltage to 25 V. Scanning electron microscopy shows that the one-dimensional nanostructure has a tubular configuration with an inner diameter of approximately 60 nm and an outer diameter of approximately 100 nm. The electrical properties of these materials were analyzed through dielectric spectroscopy method.

Spectroscopic and Electrochemical Studies of the Transition Metal Tetrasulfonated Phthalocyanines. Part 5. Voltammetric Studies of Adsorbed Tetrasulfonated Phthalocyanines (MTsPc) in Aqueous Solutions.

DTIC Science & Technology

1985-10-01

atmosphere Immediately after addition of M-TsPc to the supporting electrolyte, the first potential sweep over the given range (e.g., -0.8 to 0.3 V vs. SCE...vs. a-Pd/H electrode) at a sweep rate of 100 mV/s, voltammetric peaks of the hydrogen adsorption/desorption and oxide forma- tion/reduction processes...high sweep rates, e.g., 20 V/s. An OPG electrode standing at open-circuit potential in a Fe(III)-TsPc at potentials between peaks 3 and 4 in Fig. 1

In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

PubMed

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-free supercapacitor with aqueous electrolyte and low-cost carbon materials

NASA Astrophysics Data System (ADS)

Blomquist, Nicklas; Wells, Thomas; Andres, Britta; Bäckström, Joakim; Forsberg, Sven; Olin, Håkan

2017-01-01

Electric double-layer capacitors (EDLCs) or supercapacitors (SCs) are fast energy storage devices with high pulse efficiency and superior cyclability, which makes them useful in various applications including electronics, vehicles and grids. Aqueous SCs are considered to be more environmentally friendly than those based on organic electrolytes. Because of the corrosive nature of the aqueous environment, however, expensive electrochemically stable materials are needed for the current collectors and electrodes in aqueous SCs. This results in high costs for a given energy-storage capacity. To address this, we developed a novel low-cost aqueous SC using graphite foil as the current collector and a mix of graphene, nanographite, simple water-purification carbons and nanocellulose as electrodes. The electrodes were coated directly onto the graphite foil by using casting frames and the SCs were assembled in a pouch cell design. With this approach, we achieved a material cost reduction of greater than 90% while maintaining approximately one-half of the specific capacitance of a commercial unit, thus demonstrating that the proposed SC can be an environmentally friendly, low-cost alternative to conventional SCs.

A Study of Carbon Nanofibers and Active Carbon as Symmetric Supercapacitor in Aqueous Electrolyte: A Comparative Study

NASA Astrophysics Data System (ADS)

Daraghmeh, Allan; Hussain, Shahzad; Saadeddin, Iyad; Servera, Llorenç; Xuriguera, Elena; Cornet, Albert; Cirera, Albert

2017-12-01

Symmetric supercapacitors are fabricated by carbon nanofibers (CNF) and activated carbon (AC) using similar proportions of 7 wt% polyvinylidene fluoride (PVDF) polymer binder in an aqueous electrolyte. In this study, a comparison of porous texture and electrochemical performances between CNFs and AC based supercapacitors was carried out. Electrodes were assembled in the cell without a current collector. The prepared electrodes of CNFs and AC present Brunauer-Emmett-Teller (BET) surface area of 83 and 1042 m2/g, respectively. The dominant pore structure for CNFs is mesoporous while for AC is micropore. The results showed that AC provided higher specific capacitance retention up to very fast scan rate of 500 mV/s. AC carbon had a specific capacitance of 334 F/g, and CNFs had 52 F/g at scan rate 5 mV/s in aqueous solution. Also, the results indicate the superior conductivity of CNFs in contrast to AC counterparts. The measured equivalent series resistance (ESR) showed a very small value for CNFs (0.28 Ω) in comparison to AC that has an ESR resistance of (3.72 Ω). Moreover, CNF delivered higher specific power (1860 W/kg) than that for AC (450 W/kg). On the other hand, AC gave higher specific energy (18.1 Wh/kg) than that for CNFs (2 Wh/kg).This indicates that the AC is good for energy applications. Whereas, CNF is good for power application. Indeed, the higher surface area will lead to higher specific capacitance and hence higher energy density for AC. For CNF, lower ESR is responsible for having higher power density. Both CNF and AC supercapacitor exhibit an excellent charge-discharge stability up to 2500 cycles.

Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode: influence of experimental parameters on degradation kinetics and mineralization efficiency.

PubMed

Ozcan, Ali; Sahin, Yücel; Koparal, A Savaş; Oturan, Mehmet A

2008-06-01

This study aims the removal of a carbamate herbicide, propham, from aqueous solution by direct electrochemical advanced oxidation process using a boron-doped diamond (BDD) anode. This electrode produces large quantities of hydroxyl radicals from oxidation of water, which leads to the oxidative degradation of propham up to its total mineralization. Effect of operational parameters such as current, temperature, pH and supporting electrolyte on the degradation and mineralization rate was studied. The applied current and temperature exert a prominent effect on the total organic carbon (TOC) removal rate of the solutions. The mineralization of propham can be performed at any pH value between 3 and 11 without any loss in oxidation efficiency. The propham decay and its overall mineralization reaction follows a pseudo-first-order kinetics. The apparent rate constant value of propham oxidation was determined as 4.8 x 10(-4)s(-1) at 100 mA and 35 degrees C in the presence of 50mM Na(2)SO(4) in acidic media (pH: 3). A general mineralization sequence was proposed considering the identified oxidation intermediates.

Exfoliation of graphite into graphene in aqueous solutions of inorganic salts.

PubMed

Parvez, Khaled; Wu, Zhong-Shuai; Li, Rongjin; Liu, Xianjie; Graf, Robert; Feng, Xinliang; Müllen, Klaus

2014-04-23

Mass production of high-quality graphene sheets is essential for their practical application in electronics, optoelectronics, composite materials, and energy-storage devices. Here we report a prompt electrochemical exfoliation of graphene sheets into aqueous solutions of different inorganic salts ((NH4)2SO4, Na2SO4, K2SO4, etc.). Exfoliation in these electrolytes leads to graphene with a high yield (>85%, ≤3 layers), large lateral size (up to 44 μm), low oxidation degree (a C/O ratio of 17.2), and a remarkable hole mobility of 310 cm(2) V(-1) s(-1). Further, highly conductive graphene films (11 Ω sq(-1)) are readily fabricated on an A4-size paper by applying brush painting of a concentrated graphene ink (10 mg mL(-1), in N,N'-dimethylformamide). All-solid-state flexible supercapacitors manufactured on the basis of such graphene films deliver a high area capacitance of 11.3 mF cm(-2) and an excellent rate capability of 5000 mV s(-1). The described electrochemical exfoliation shows great promise for the industrial-scale synthesis of high-quality graphene for numerous advanced applications.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, K.O.

1998-06-30

A polymer bonded sheet product is described suitable for use as an electrode in a non-aqueous battery system. A porous electrode sheet is impregnated with a solid polymer electrolyte, so as to diffuse into the pores of the electrode. The composite is allowed to cool, and the electrolyte is entrapped in the porous electrode. The sheet products composed have the solid polymer electrolyte composition diffused into the active electrode material by melt-application of the solid polymer electrolyte composition into the porous electrode material sheet. The solid polymer electrolyte is maintained at a temperature that allows for rapid diffusion into the pores of the electrode. The composite electrolyte-electrode sheets are formed on current collectors and can be coated with solid polymer electrolyte prior to battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte coating has low resistance. 1 fig.

Anomalies in the equilibrium and nonequilibrium properties of correlated ions in complex molecular environments

NASA Astrophysics Data System (ADS)

Mahakrishnan, Sathiya; Chakraborty, Subrata; Vijay, Amrendra

2017-11-01

Emergent statistical attributes, and therefore the equations of state, of an assembly of interacting charge carriers embedded within a complex molecular environment frequently exhibit a variety of anomalies, particularly in the high-density (equivalently, the concentration) regime, which are not well understood, because they do not fall under the low-concentration phenomenologies of Debye-Hückel-Onsager and Poisson-Nernst-Planck, including their variants. To go beyond, we here use physical concepts and mathematical tools from quantum scattering theory, transport theory with the Stosszahlansatz of Boltzmann, and classical electrodynamics (Lorentz gauge) and obtain analytical expressions both for the average and the frequency-wave vector-dependent longitudinal and transverse current densities, diffusion coefficient, and the charge density, and therefore the analytical expressions for (a) the chemical potential, activity coefficient, and the equivalent conductivity for strong electrolytes and (b) the current-voltage characteristics for ion-transport processes in complex molecular environments. Using a method analogous to the notion of Debye length and thence the electrical double layer, we here identify a pair of characteristic length scales (longitudinal and the transverse), which, being wave vector and frequency dependent, manifestly exhibit nontrivial fluctuations in space-time. As a unifying theme, we advance a quantity (inverse length dimension), gscat(a ), which embodies all dynamical interactions, through various quantum scattering lengths, relevant to molecular species a, and the analytical behavior which helps us to rationalize the properties of strong electrolytes, including anomalies, in all concentration regimes. As an example, the behavior of gscat(a ) in the high-concentration regime explains the anomalous increase of the Debye length with concentration, as seen in a recent experiment on electrolyte solutions. We also put forth an extension of the standard diffusion equation, which manifestly incorporates the effects arising from the underlying microscopic collisions among constituent molecular species. Furthermore, we show a nontrivial connection between the current-voltage characteristics of electrolyte solutions and the Landauer's approach to electrical conduction in mesoscopic solids and thereby establish a definite conceptual bridge between the two disjoint subjects. For numerical insight, we present results on the aqueous solution of KCl as an example of strong electrolyte, and the transport (conduction as well as diffusion) of K+ ions in water, as an example of ion transport across the voltage-gated channels in biological cells.

Anomalies in the equilibrium and nonequilibrium properties of correlated ions in complex molecular environments.

PubMed

Mahakrishnan, Sathiya; Chakraborty, Subrata; Vijay, Amrendra

2017-11-01

Emergent statistical attributes, and therefore the equations of state, of an assembly of interacting charge carriers embedded within a complex molecular environment frequently exhibit a variety of anomalies, particularly in the high-density (equivalently, the concentration) regime, which are not well understood, because they do not fall under the low-concentration phenomenologies of Debye-Hückel-Onsager and Poisson-Nernst-Planck, including their variants. To go beyond, we here use physical concepts and mathematical tools from quantum scattering theory, transport theory with the Stosszahlansatz of Boltzmann, and classical electrodynamics (Lorentz gauge) and obtain analytical expressions both for the average and the frequency-wave vector-dependent longitudinal and transverse current densities, diffusion coefficient, and the charge density, and therefore the analytical expressions for (a) the chemical potential, activity coefficient, and the equivalent conductivity for strong electrolytes and (b) the current-voltage characteristics for ion-transport processes in complex molecular environments. Using a method analogous to the notion of Debye length and thence the electrical double layer, we here identify a pair of characteristic length scales (longitudinal and the transverse), which, being wave vector and frequency dependent, manifestly exhibit nontrivial fluctuations in space-time. As a unifying theme, we advance a quantity (inverse length dimension), g_{scat}^{(a)}, which embodies all dynamical interactions, through various quantum scattering lengths, relevant to molecular species a, and the analytical behavior which helps us to rationalize the properties of strong electrolytes, including anomalies, in all concentration regimes. As an example, the behavior of g_{scat}^{(a)} in the high-concentration regime explains the anomalous increase of the Debye length with concentration, as seen in a recent experiment on electrolyte solutions. We also put forth an extension of the standard diffusion equation, which manifestly incorporates the effects arising from the underlying microscopic collisions among constituent molecular species. Furthermore, we show a nontrivial connection between the current-voltage characteristics of electrolyte solutions and the Landauer's approach to electrical conduction in mesoscopic solids and thereby establish a definite conceptual bridge between the two disjoint subjects. For numerical insight, we present results on the aqueous solution of KCl as an example of strong electrolyte, and the transport (conduction as well as diffusion) of K^{+} ions in water, as an example of ion transport across the voltage-gated channels in biological cells.