New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions.

PubMed

Romanenko, Konstantin; Pringle, Jennifer M; O'Dell, Luke A; Forsyth, Maria

2015-07-15

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

Friction and wear behavior of glasses and ceramics

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Adhesion, friction, and wear behavior of glasses and ionic solids are reviewed. These materials are shown to behave in a manner similar to other solids with respect to adhesion. Their friction characteristics are shown to be sensitive to environmental constituents and surface films. This sensitivity can be related to a reduction in adhesive bonding and the changes in surficial mechanical behavior associated with Rehbinder and Joffe effects. Both friction and wear properties of ionic crystalline solids are highly anisotropic. With metals in contact with ionic solids the fracture strength of the ionic solid and the shear strength in the metal and those properties that determine these will dictate which of the materials undergoes adhesive wear. The chemical activity of the metal plays an important role in the nature and strength of the adhesive interfacial bond that develops between the metal and a glass or ionic solid.

Effects of anisotropic electron-ion interactions in atomic photoelectron angular distributions

NASA Technical Reports Server (NTRS)

Dill, D.; Starace, A. F.; Manson, S. T.

1975-01-01

A summary of the angular momentum transfer formulation of the differential photoionization cross section is presented and photoionization amplitudes in LS coupling are considered. The application of the theoretical concepts and relations developed is illustrated with the aid of an example involving the calculation of the angular distribution of photoelectrons ionized from atomic sulfur according to a certain reaction. The investigation shows that anisotropic electron-ion interactions in atomic sulfur lead to measurable differences between photoelectron angular distribution asymmetry parameters corresponding to alternative ionic term levels.

Phase transition in 2-d system of quadrupoles on square lattice with anisotropic field

NASA Astrophysics Data System (ADS)

Sallabi, A. K.; Alkhttab, M.

2014-12-01

Monte Carlo method is used to study a simple model of two-dimensional interacting quadrupoles on ionic square lattice with anisotropic strength provided by the ionic lattice. Order parameter, susceptibility and correlation function data, show that this system form an ordered structure with p(2×1) symmetry at low temperature. The p(2×1) structure undergoes an order-disorder phase transition into disordered (1×1) phase at 8.3K. The two-point correlation function show exponential dependence on distance both above and below the transition temperature. At Tc the two-point correlation function shows a power law dependence on distance, e.g. C(r) ~ 1η. The value of the exponent η at Tc shows small deviation from the Ising value and indicates that this system falls into the same universality class as the XY model with cubic anisotropy. This model can be applied to prototypical quadrupoles physisorbed systems as N2 on NaCl(100).

Anisotropic conductivity imaging with MREIT using equipotential projection algorithm.

PubMed

Değirmenci, Evren; Eyüboğlu, B Murat

2007-12-21

Magnetic resonance electrical impedance tomography (MREIT) combines magnetic flux or current density measurements obtained by magnetic resonance imaging (MRI) and surface potential measurements to reconstruct images of true conductivity with high spatial resolution. Most of the biological tissues have anisotropic conductivity; therefore, anisotropy should be taken into account in conductivity image reconstruction. Almost all of the MREIT reconstruction algorithms proposed to date assume isotropic conductivity distribution. In this study, a novel MREIT image reconstruction algorithm is proposed to image anisotropic conductivity. Relative anisotropic conductivity values are reconstructed iteratively, using only current density measurements without any potential measurement. In order to obtain true conductivity values, only either one potential or conductivity measurement is sufficient to determine a scaling factor. The proposed technique is evaluated on simulated data for isotropic and anisotropic conductivity distributions, with and without measurement noise. Simulation results show that the images of both anisotropic and isotropic conductivity distributions can be reconstructed successfully.

Dipole estimation errors due to not incorporating anisotropic conductivities in realistic head models for EEG source analysis

NASA Astrophysics Data System (ADS)

Hallez, Hans; Staelens, Steven; Lemahieu, Ignace

2009-10-01

EEG source analysis is a valuable tool for brain functionality research and for diagnosing neurological disorders, such as epilepsy. It requires a geometrical representation of the human head or a head model, which is often modeled as an isotropic conductor. However, it is known that some brain tissues, such as the skull or white matter, have an anisotropic conductivity. Many studies reported that the anisotropic conductivities have an influence on the calculated electrode potentials. However, few studies have assessed the influence of anisotropic conductivities on the dipole estimations. In this study, we want to determine the dipole estimation errors due to not taking into account the anisotropic conductivities of the skull and/or brain tissues. Therefore, head models are constructed with the same geometry, but with an anisotropically conducting skull and/or brain tissue compartment. These head models are used in simulation studies where the dipole location and orientation error is calculated due to neglecting anisotropic conductivities of the skull and brain tissue. Results show that not taking into account the anisotropic conductivities of the skull yields a dipole location error between 2 and 25 mm, with an average of 10 mm. When the anisotropic conductivities of the brain tissues are neglected, the dipole location error ranges between 0 and 5 mm. In this case, the average dipole location error was 2.3 mm. In all simulations, the dipole orientation error was smaller than 10°. We can conclude that the anisotropic conductivities of the skull have to be incorporated to improve the accuracy of EEG source analysis. The results of the simulation, as presented here, also suggest that incorporation of the anisotropic conductivities of brain tissues is not necessary. However, more studies are needed to confirm these suggestions.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures.

PubMed

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina; Schröder, Christian

2017-01-13

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C 2 mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood-Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed.

A comparison study of the Born effective charges and dielectric properties of the cubic, tetragonal, monoclinic, ortho-I, ortho-II and ortho-III phases of zirconia

NASA Astrophysics Data System (ADS)

Zhang, Yan; Chen, Hua-Xin; Duan, Li; Fan, Ji-Bin; Ni, Lei; Ji, Vincent

2018-07-01

Using density-functional perturbation theory, we systematically investigate the Born effective charges and dielectric properties of cubic, tetragonal, monoclinic, ortho-I (Pbca), ortho-II (Pnma) and ortho-III (Pca21) phases of ZrO2. The magnitudes of the Born effective charges of the Zr and oxygen atoms are greater than their nominal ionic valences (+4 for Zr and -2 for oxygen), indicating a strong dynamic charge transfer from Zr atoms to O atoms and a mixed covalent-ionic bonding in six phases of ZrO2. For all six phases of ZrO2, the electronic contributions εij∞ to the static dielectric constant are rather small (range from 5 to 6.5) and neither strongly anisotropic nor strongly dependent on the structural phase, while the ionic contributions εijion to the static dielectric constant are large and not only anisotropic but also dependent on the structural phase. The average dielectric constant εbar0 of the six ZrO2 phases decreases in the sequence of tetragonal, cubic, ortho-II (Pnma), ortho-I (Pbca), ortho-III (Pca21) and monoclinic. So among six phases of ZrO2, the tetragonal and cubic phases are two suitable phases to replace SiO2 as the gate dielectric material in modern integrated-circuit technology. Furthermore, for the tetragonal ZrO2 the best orientation is [100].

Polarity governed selective amplification of through plane proton shuttling in proton exchange membrane fuel cells.

PubMed

Gautam, Manu; Chattanahalli Devendrachari, Mruthyunjayachari; Thimmappa, Ravikumar; Raja Kottaichamy, Alagar; Pottachola Shafi, Shahid; Gaikwad, Pramod; Makri Nimbegondi Kotresh, Harish; Ottakam Thotiyl, Musthafa

2017-03-15

Graphene oxide (GO) anisotropically conducts protons with directional dominance of in plane ionic transport (σ IP) over the through plane (σ TP). In a typical H 2 -O 2 fuel cell, since the proton conduction occurs through the plane during its generation at the fuel electrode, it is indeed inevitable to selectively accelerate GO's σ TP for advancement towards a potential fuel cell membrane. We successfully achieved ∼7 times selective amplification of GO's σ TP by tuning the polarity of the dopant molecule in its nanoporous matrix. The coexistence of strongly non-polar and polar domains in the dopant demonstrated a synergistic effect towards σ TP with the former decreasing the number of water molecules coordinated to protons by ∼3 times, diminishing the effects of electroosmotic drag exerted on ionic movements, and the latter selectively accelerating σ TP across the catalytic layers by bridging the individual GO planes via extensive host guest H-bonding interactions. When they are decoupled, the dopant with mainly non-polar or polar features only marginally enhances the σ TP, revealing that polarity factors contribute to fuel cell relevant transport properties of GO membranes only when they coexist. Fuel cell polarization and kinetic analyses revealed that these multitask dopants increased the fuel cell performance metrics of the power and current densities by ∼3 times compared to the pure GO membranes, suggesting that the functional group factors of the dopants are of utmost importance in GO-based proton exchange membrane fuel cells.

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes

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

Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEsmore » with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per mu m(2) to 20 terminal defects per mu m(2) ( a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.« less

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra24736a Click here for additional data file.

PubMed Central

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina

2017-01-01

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood–Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed. PMID:28496974

Effect of electron-hole asymmetry on optical conductivity in 8 -P m m n borophene

NASA Astrophysics Data System (ADS)

Verma, Sonu; Mawrie, Alestin; Ghosh, Tarun Kanti

2017-10-01

We present a detailed theoretical study of the Drude weight and optical conductivity of 8-P m m n borophene having tilted anisotropic Dirac cones. We provide exact analytical expressions of x x and y y components of the Drude weight as well as maximum optical conductivity. We also obtain exact analytical expressions of the minimum energy (ɛ1) required to trigger the optical transitions and energy (ɛ2) needed to attain maximum optical conductivity. We find that the Drude weight and optical conductivity are highly anisotropic as a consequence of the anisotropic Dirac cone. The optical conductivities have a nonmonotonic behavior with photon energy in the regime between ɛ1 and ɛ2, as a result of the tilted parameter vt. The tilted parameter can be extracted by knowing ɛ1 and ɛ2 from optical measurements. The maximum values of the components of the optical conductivity do not depend on the carrier density and the tilted parameter. The product of the maximum values of the anisotropic conductivities has the universal value (e2/4ℏ ) 2. The tilted anisotropic Dirac cones in 8-P m m n borophene can be realized by the optical conductivity measurement.

Dynamic Octahedral Breathing in Oxygen-Deficient Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) Perovskite Performing as a Cathode in Intermediate-Temperature SOFC.

PubMed

Gong, Yudong; Sun, Chunwen; Huang, Qiu-an; Alonso, Jose Antonio; Fernández-Díaz, Maria Teresa; Chen, Liquan

2016-03-21

Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) outperforms as a cathode in solid-oxide fuel cells (SOFC), at temperatures as low as 700-750 °C. The microscopical reason for this performance was investigated by temperature-dependent neutron powder diffraction (NPD) experiments. In the temperature range of 25-800 °C, Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) shows a perfectly cubic structure (a = a0), with a significant oxygen deficiency in a single oxygen site, that substantially increases at the working temperatures of a SOFC. The anisotropic thermal motion of oxygen atoms considerably rises with T, reaching B(eq) ≈ 5 Å(2) at 800 °C, with prolate cigar-shaped, anisotropic vibration ellipsoids that suggest a dynamic breathing of the octahedra as oxygen ions diffuse across the structure by a vacancies mechanism, thus implying a significant ionic mobility that could be described as a molten oxygen sublattice. The test cell with a La(0.8)Sr(0.2)Ga(0.83)Mg(0.17)O(3-δ) electrolyte (∼300 μm in thickness)-supported configuration yields a peak power density of 0.20 and 0.40 W cm(-2) at temperatures of 700 and 750 °C, respectively, with pure H2 as fuel and ambient air as oxidant. The electrochemical impedance spectra (EIS) evolution with time of the symmetric cathode fuel cell measured at 750 °C shows that the Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) cathode possesses a superior ORR catalytic activity and long-term stability. The mixed electronic-ionic conduction properties of Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) account for its good performance as an oxygen-reduction catalyst.

Illusion thermal device based on material with constant anisotropic thermal conductivity for location camouflage

NASA Astrophysics Data System (ADS)

Hou, Quanwen; Zhao, Xiaopeng; Meng, Tong; Liu, Cunliang

2016-09-01

Thermal metamaterials and devices based on transformation thermodynamics often require materials with anisotropic and inhomogeneous thermal conductivities. In this study, still based on the concept of transformation thermodynamics, we designed a planar illusion thermal device, which can delocalize a heat source in the device such that the temperature profile outside the device appears to be produced by a virtual source at another position. This device can be constructed by only one kind of material with constant anisotropic thermal conductivity. The condition which should be satisfied by the device is provided, and the required anisotropic thermal conductivity is then deduced theoretically. This study may be useful for the designs of metamaterials or devices since materials with constant anisotropic parameters have great facility in fabrication. A prototype device has been fabricated based on a composite composed by two naturally occurring materials. The experimental results validate the effectiveness of the device.

Theory of anisotropic hybridization-broadened magnetic response in cerium and actinide systems

NASA Astrophysics Data System (ADS)

Hu, Gong-Jia; Cooper, Bernard R.

1993-11-01

Inelastic-neutron-scattering measurements on cerium and plutonium monopnictides, thought to have moderately delocalized f electrons, yield magnetic-excitation spectra with anisotropic dispersion; while reasonably sharp excitations have been observed only for USb and UTe among presumably more-delocalized uranium monopnictides and monochalcogenides. For UTe the broadening as well as the dispersion is quite anisotropic. We have now extended our previous theory for the magnetic behavior of hybridizing partially delocalized f-electron systems to include hybridization-induced relaxation effects in the magnetic response, and this work and results are reported in the present paper. Each partially delocalized f-electron ion is coupled by hybridization to the band sea; and this both leads to a hybridization-mediated anisotropic two-ion interaction giving magnetic ordering and also gives a damping mechanism, via the coupling to the band sea, for the excitations of the magnetically ordered lattice. This coupling also provides a strong renormalization of the magnetic-excitation energies obtained for the ionic lattice coupled by the two-ion interaction. To treat these effects on the magnetic response we have developed a formalism for calculating the dynamic susceptibility based on the projection-operator method developed by Mori and others. We have applied our model and theory to the behavior of CeSb, CeBi, PuSb, UP, UAs, and UTe; and excellent overall agreement with the wide range of unusual experimentally observed anisotropic magnetic-excitation behavior is obtained.

Determining anisotropic conductivity using diffusion tensor imaging data in magneto-acoustic tomography with magnetic induction

NASA Astrophysics Data System (ADS)

Ammari, Habib; Qiu, Lingyun; Santosa, Fadil; Zhang, Wenlong

2017-12-01

In this paper we present a mathematical and numerical framework for a procedure of imaging anisotropic electrical conductivity tensor by integrating magneto-acoutic tomography with data acquired from diffusion tensor imaging. Magneto-acoustic tomography with magnetic induction (MAT-MI) is a hybrid, non-invasive medical imaging technique to produce conductivity images with improved spatial resolution and accuracy. Diffusion tensor imaging (DTI) is also a non-invasive technique for characterizing the diffusion properties of water molecules in tissues. We propose a model for anisotropic conductivity in which the conductivity is proportional to the diffusion tensor. Under this assumption, we propose an optimal control approach for reconstructing the anisotropic electrical conductivity tensor. We prove convergence and Lipschitz type stability of the algorithm and present numerical examples to illustrate its accuracy and feasibility.

Double anisotropic electrically conductive flexible Janus-typed membranes.

PubMed

Li, Xiaobing; Ma, Qianli; Tian, Jiao; Xi, Xue; Li, Dan; Dong, Xiangting; Yu, Wensheng; Wang, Xinlu; Wang, Jinxian; Liu, Guixia

2017-12-07

Novel type III anisotropic conductive films (ACFs), namely flexible Janus-typed membranes, were proposed, designed and fabricated for the first time. Flexible Janus-typed membranes composed of ordered Janus nanobelts were constructed by electrospinning, which simultaneously possess fluorescence and double electrically conductive anisotropy. For the fabrication of the Janus-typed membrane, Janus nanobelts comprising a conductive side and an insulative-fluorescent side were primarily fabricated, and then the Janus nanobelts are arranged into parallel arrays using an aluminum rotary drum as the collector to obtain a single anisotropically conductive film. Subsequently, a secondary electrospinning process was applied to the as-prepared single anisotropically conductive films to acquire the final Janus-typed membrane. For this Janus-typed membrane, namely its left-to-right structure, anisotropic electrical conduction synchronously exists on both sides, and furthermore, the two electrically conductive directions are perpendicular. By modulating the amount of Eu(BA) 3 phen complex and conducting polyaniline (PANI), the characteristics and intensity of the fluorescence-electricity dual-function in the membrane can be tuned. The high integration of this peculiar Janus-typed membrane with simultaneous double electrically conductive anisotropy-fluorescent dual-functionality is successfully realized in this study. This design philosophy and preparative technique will provide support for the design and construction of new types of special nanostructures with multi-functionality.

A review of anisotropic conductivity models of brain white matter based on diffusion tensor imaging.

PubMed

Wu, Zhanxiong; Liu, Yang; Hong, Ming; Yu, Xiaohui

2018-06-01

The conductivity of brain tissues is not only essential for electromagnetic source estimation (ESI), but also a key reflector of the brain functional changes. Different from the other brain tissues, the conductivity of whiter matter (WM) is highly anisotropic and a tensor is needed to describe it. The traditional electrical property imaging methods, such as electrical impedance tomography (EIT) and magnetic resonance electrical impedance tomography (MREIT), usually fail to image the anisotropic conductivity tensor of WM with high spatial resolution. The diffusion tensor imaging (DTI) is a newly developed technique that can fulfill this purpose. This paper reviews the existing anisotropic conductivity models of WM based on the DTI and discusses their advantages and disadvantages, as well as identifies opportunities for future research on this subject. It is crucial to obtain the linear conversion coefficient between the eigenvalues of anisotropic conductivity tensor and diffusion tensor, since they share the same eigenvectors. We conclude that the electrochemical model is suitable for ESI analysis because the conversion coefficient can be directly obtained from the concentration of ions in extracellular liquid and that the volume fraction model is appropriate to study the influence of WM structural changes on electrical conductivity. Graphical abstract ᅟ.

3-D direct current resistivity anisotropic modelling by goal-oriented adaptive finite element methods

NASA Astrophysics Data System (ADS)

Ren, Zhengyong; Qiu, Lewen; Tang, Jingtian; Wu, Xiaoping; Xiao, Xiao; Zhou, Zilong

2018-01-01

Although accurate numerical solvers for 3-D direct current (DC) isotropic resistivity models are current available even for complicated models with topography, reliable numerical solvers for the anisotropic case are still an open question. This study aims to develop a novel and optimal numerical solver for accurately calculating the DC potentials for complicated models with arbitrary anisotropic conductivity structures in the Earth. First, a secondary potential boundary value problem is derived by considering the topography and the anisotropic conductivity. Then, two a posteriori error estimators with one using the gradient-recovery technique and one measuring the discontinuity of the normal component of current density are developed for the anisotropic cases. Combing the goal-oriented and non-goal-oriented mesh refinements and these two error estimators, four different solving strategies are developed for complicated DC anisotropic forward modelling problems. A synthetic anisotropic two-layer model with analytic solutions verified the accuracy of our algorithms. A half-space model with a buried anisotropic cube and a mountain-valley model are adopted to test the convergence rates of these four solving strategies. We found that the error estimator based on the discontinuity of current density shows better performance than the gradient-recovery based a posteriori error estimator for anisotropic models with conductivity contrasts. Both error estimators working together with goal-oriented concepts can offer optimal mesh density distributions and highly accurate solutions.

Influence of anisotropic conductivity in the skull and white matter on transcranial direct current stimulation via an anatomically realistic finite element head model

NASA Astrophysics Data System (ADS)

Suh, Hyun Sang; Lee, Won Hee; Kim, Tae-Seong

2012-11-01

To establish safe and efficient transcranial direct current stimulation (tDCS), it is of particular importance to understand the electrical effects of tDCS in the brain. Since the current density (CD) and electric field (EF) in the brain generated by tDCS depend on various factors including complex head geometries and electrical tissue properties, in this work, we investigated the influence of anisotropic conductivity in the skull and white matter (WM) on tDCS via a 3D anatomically realistic finite element head model. We systematically incorporated various anisotropic conductivity ratios into the skull and WM. The effects of anisotropic tissue conductivity on the CD and EF were subsequently assessed through comparisons to the conventional isotropic solutions. Our results show that the anisotropic skull conductivity significantly affects the CD and EF distribution: there is a significant reduction in the ratio of the target versus non-target total CD and EF on the order of 12-14%. In contrast, the WM anisotropy does not significantly influence the CD and EF on the targeted cortical surface, only on the order of 1-3%. However, the WM anisotropy highly alters the spatial distribution of both the CD and EF inside the brain. This study shows that it is critical to incorporate anisotropic conductivities in planning of tDCS for improved efficacy and safety.

Self-doped microphase separated block copolymer electrolyte

DOEpatents

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

2002-01-01

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

Ionic Liquids in Electro-active Devices (ILED)

DTIC Science & Technology

2013-12-12

Polyesters: Structure-Property Relationships in Thermal Behavior, Ionic Conductivity , and Morphology , Advanced Functional Materials, (01 2010...and Ionic Conductivities , Macromolecular Chemistry and Physics, (10 2011): . doi: M. Green, C. Schreiner, T. Long. Thermal , Rheological, and Ion...block giving thermal stability and ionic conductivity . Table 1 shows the molecular weight analysis of the triblock copolymers with increasing

Ultrahigh-throughput exfoliation of graphite into pristine 'single-layer' graphene using microwaves and molecularly engineered ionic liquids.

PubMed

Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

2015-09-01

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards 'single-layer' graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml(-1), and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Anisotropic thermal conduction with magnetic fields in galaxy clusters

NASA Astrophysics Data System (ADS)

Arth, Alexander; Dolag, Klaus; Beck, Alexander; Petkova, Margarita; Lesch, Harald

2015-08-01

Magnetic fields play an important role for the propagation and diffusion of charged particles, which are responsible for thermal conduction. In this poster, we present an implementation of thermal conduction including the anisotropic effects of magnetic fields for smoothed particle hydrodynamics (SPH). The anisotropic thermal conduction is mainly proceeding parallel to magnetic fields and suppressed perpendicular to the fields. We derive the SPH formalism for the anisotropic heat transport and solve the corresponding equation with an implicit conjugate gradient scheme. We discuss several issues of unphysical heat transport in the cases of extreme ansiotropies or unmagnetized regions and present possible numerical workarounds. We implement our algorithm into the cosmological simulation code GADGET and study its behaviour in several test cases. In general, we reproduce the analytical solutions of our idealised test problems, and obtain good results in cosmological simulations of galaxy cluster formations. Within galaxy clusters, the anisotropic conduction produces a net heat transport similar to an isotropic Spitzer conduction model with low efficiency. In contrast to isotropic conduction our new formalism allows small-scale structure in the temperature distribution to remain stable, because of their decoupling caused by magnetic field lines. Compared to observations, strong isotropic conduction leads to an oversmoothed temperature distribution within clusters, while the results obtained with anisotropic thermal conduction reproduce the observed temperature fluctuations well. A proper treatment of heat transport is crucial especially in the outskirts of clusters and also in high density regions. It's connection to the local dynamical state of the cluster also might contribute to the observed bimodal distribution of cool core and non cool core clusters. Our new scheme significantly advances the modelling of thermal conduction in numerical simulations and overall gives better results compared to observations.

Uniqueness for the electrostatic inverse boundary value problem with piecewise constant anisotropic conductivities

NASA Astrophysics Data System (ADS)

Alessandrini, Giovanni; de Hoop, Maarten V.; Gaburro, Romina

2017-12-01

We discuss the inverse problem of determining the, possibly anisotropic, conductivity of a body Ω\\subset{R}n when the so-called Neumann-to-Dirichlet map is locally given on a non-empty curved portion Σ of the boundary \\partialΩ . We prove that anisotropic conductivities that are a priori known to be piecewise constant matrices on a given partition of Ω with curved interfaces can be uniquely determined in the interior from the knowledge of the local Neumann-to-Dirichlet map.

Optimization of neural network for ionic conductivity of nanocomposite solid polymer electrolyte system (PEO-LiPF 6-EC-CNT)

NASA Astrophysics Data System (ADS)

Johan, Mohd Rafie; Ibrahim, Suriani

2012-01-01

In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF 6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF 6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system's accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.

Correlation between ion diffusional motion and ionic conductivity for different electrolytes based on ionic liquid.

PubMed

Kaur, Dilraj Preet; Yamada, K; Park, Jin-Soo; Sekhon, S S

2009-04-23

Room temperature ionic liquid 2,3-dimethyl-1-hexylimidazolium bis(trifluoromethane sulfonyl)imide (DMHxImTFSI) has been synthesized and used in the preparation of polymer gel electrolytes containing polymethylmethacrylate and propylene carbonate (PC). The onset of ion diffusional motion has been studied by (1)H and (19)F NMR spectroscopy and the results obtained for ionic liquid, liquid electrolytes, and polymer gel electrolytes have been correlated with the ionic conductivity results for these electrolytes in the 100-400 K temperature range. The temperature at which (1)H and (19)F NMR lines show motional narrowing and hence ion diffusional motion starts has been found to be closely related to the temperature at which a large increase in ionic conductivity has been observed for these electrolytes. Polymer gel electrolytes have high ionic conductivity over a wide range of temperatures. Thermogravimetric analysis/differential scanning calorimetry studies show that the ionic liquid (DMHxImTFSI) used in the present study is thermally stable up to 400 degrees C, whereas the addition of PC lowers the thermal stability of polymer gel electrolytes containing the ionic liquid. Different electrolytes have been observed to show high ionic conductivity in different range of temperatures, which can be helpful in the design of polymer gel electrolytes for specific applications.

The role of anisotropic thermal conduction in a collisionless magnetized hot accretion flow

NASA Astrophysics Data System (ADS)

Ghasemnezhad, Maryam

2018-06-01

We study the importance and the effects of anisotropic thermal conduction in a collisionless magnetized advection dominated accretion flow in the presence of discontinuity of mass, angular momentum and energy between inflow and outflow. In this paper, we have considered that the thermal conduction is a heating mechanism like viscosity and leads to an increase in the temperature of the gas. A set of self similar solutions are used for steady state and axisymmetric structure of such hot accretion disc to solve the MHD equations in our model. Based on these solutions, we have found that increasing the level of two parts of anisotropic thermal conduction (parallel & transverse) results in increasing the mass accretion rate or radial velocity but decreasing the rotational velocity. Also both radial and rotational velocities are sub-Keplerian. Also we have shown that the anisotropic thermal conduction can be effective in the parameter space of specific energy of outflow, toroidal and vertical components of magnetic field according to a physical constraint tinfall ≥ t⊥, conduction.

The Evaporation and Survival of Cluster Galaxies’ Coronae. II. The Effectiveness of Anisotropic Thermal Conduction and Survival of Stripped Galactic Tails

NASA Astrophysics Data System (ADS)

Vijayaraghavan, Rukmani; Sarazin, Craig

2017-10-01

We simulate anisotropic thermal conduction between the intracluster medium (ICM) and the hot coronal interstellar medium (ISM) gas in cluster galaxies. In Paper I, we simulated the evaporation of the hot ISM due to isotropic (possibly saturated) conduction between the ISM and ICM. We found that hot coronae evaporate on ˜ {10}2 {Myr} timescales, significantly shorter than the ˜ {10}3 {Myr} gas loss times due to ram pressure stripping. No tails of stripped gas are formed. This is in tension with the observed ubiquity and implied longevity of compact X-ray coronae and stripped ISM tails, and requires the suppression of evaporation, possibly due to magnetic fields and anisotropic conduction. We perform a series of wind tunnel simulations similar to that in Paper I, now including ISM and ICM magnetic fields. We simulate the effect of anisotropic conduction for a range of extreme magnetic field configurations: parallel and perpendicular to the ICM wind, and continuous and completely disjointed between the ISM and ICM. We find that when conduction is anisotropic, gas loss due to evaporation is severely reduced; the overall gas loss rates with and without anisotropic conduction do not differ by more than 10%-20%. Magnetic fields also prevent stripped tails from evaporating in the ICM by shielding, and providing few pathways for heat transport between the ICM and ISM. The morphology of stripped tails and magnetic fields in the tails and wakes of galaxies are sensitive to the initial magnetic field configuration.

Highly efficient conductivity modulation of cinnamate-based light-responsive ionic liquids in aqueous solutions.

PubMed

Yang, Jie; Wang, Huiyong; Wang, Jianji; Zhang, Yue; Guo, Zhongjia

2014-12-11

A new class of cinnamate-based light-responsive ionic liquids was synthesized and characterized, and these ionic liquids with longer alkyl chains showed a remarkable increase in ionic conductivity under UV light irradiation in aqueous solutions.

Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

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

He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.

2011-08-01

The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationshipmore » between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.« less

Communication: Influence of nanophase segregation on ion transport in room temperature ionic liquids

DOE PAGES

Griffin, Philip J.; Wang, Yangyang; Holt, Adam P.; ...

2016-04-21

In this paper, we report measurements of the ionic conductivity, shear viscosity, and structural dynamics in a homologous series of quaternary ammonium ionic liquids (ILs) and a prototypical imidazolium-based IL over a wide range of temperatures down to the glass transition. We find that the ionic conductivity of these materials generally decreases, while the shear viscosity correspondingly increases, with increasing volume fraction of aliphatic side groups. Upon crossing an aliphatic volume fraction of ~0.40, we observe a sharp, order-of-magnitude decrease in ionic conductivity and enhancement of viscosity, which coincides with the presence of long-lived, nanometer-sized alkyl aggregates. These strong changesmore » in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Finally, our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.« less

Geometric phase and o -mode blueshift in a chiral anisotropic medium inside a Fabry-Pérot cavity

NASA Astrophysics Data System (ADS)

Timofeev, Ivan V.; Gunyakov, Vladimir A.; Sutormin, Vitaly S.; Myslivets, Sergey A.; Arkhipkin, Vasily G.; Vetrov, Stepan Ya.; Lee, Wei; Zyryanov, Victor Ya.

2015-11-01

Anomalous spectral shift of transmission peaks is observed in a Fabry-Pérot cavity filled with a chiral anisotropic medium. The effective refractive index value resides out of the interval between the ordinary and the extraordinary refractive indices. The spectral shift is explained by contribution of a geometric phase. The problem is solved analytically using the approximate Jones matrix method, numerically using the accurate Berreman method, and geometrically using the generalized Mauguin-Poincaré rolling cone method. The o -mode blueshift is measured for a 4-methoxybenzylidene-4 '-n -butylaniline twisted-nematic layer inside the Fabry-Pérot cavity. The twist is electrically induced due to the homeoplanar-twisted configuration transition in an ionic-surfactant-doped liquid crystal layer. Experimental evidence confirms the validity of the theoretical model.

Structure, ionic conductivity and mobile carrier density in fast ionic conducting chalcogenide glasses

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

Yao, Wenlong

2006-01-01

This thesis consists of six sections. The first section gives the basic research background on the ionic conduction mechanism in glass, polarization in the glass, and the method of determining the mobile carrier density in glass. The proposed work is also included in this section. The second section is a paper that characterizes the structure of MI + M 2S + (0.1 Ga 2S 3 + 0.9 GeS 2) (M = Li, Na, K and Cs) glasses using Raman and IR spectroscopy. Since the ionic radius plays an important role in determining the ionic conductivity in glasses, the glass formingmore » range for the addition of different alkalis into the basic glass forming system 0.1 Ga 2S 3 + 0.9 GeS 2 was studied. The study found that the change of the alkali radius for the same nominal composition causes significant structure change to the glasses. The third section is a paper that investigates the ionic conductivity of MI + M 2S + (0.1Ga 2S 3 + 0.9 GeS 2) (M = Li, Na, K and Cs) glasses system. Corresponding to the compositional changes in these fast ionic conducting glasses, the ionic conductivity shows changes due to the induced structural changes. The ionic radius effect on the ionic conductivity in these glasses was investigated. The fourth section is a paper that examines the mobile carrier density based upon the measurements of space charge polarization. For the first time, the charge carrier number density in fast ionic conducting chalcogenide glasses was determined. The experimental impedance data were fitted using equivalent circuits and the obtained parameters were used to determine the mobile carrier density. The influence of mobile carrier density and mobility on the ionic conductivity was separated. The fifth section is a paper that studies the structures of low-alkali-content Na 2S + B 2S 3 (x ≤ 0.2) glasses by neutron and synchrotron x-ray diffraction. Similar results were obtained both in neutron and synchrotron x-ray diffraction experiments. The results provide direct structural evidence that doping B 2S 3 with Na 2S creates a large fraction of tetrahedrally coordinated boron in the glass. The final section is the general conclusion of this thesis and the suggested future work that could be conducted to expand upon this research.« less

Anisotropic thermal conductivity of thin polycrystalline oxide samples

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

Tiwari, A., E-mail: abhishektiwariiitr@gmail.com; Department of Mechanical and Aerospace Engineering, Monash University, Melbourne, VIC 3800; Boussois, K.

2013-11-15

This paper reports about the development of a modified laser-flash technique and relation to measure the in-plane thermal diffusivity of thin polycrystalline oxide samples. Thermal conductivity is then calculated with the product of diffusivity, specific heat and density. Design and operating features for evaluating in-plane thermal conductivities are described. The technique is advantageous as thin samples are not glued together to measure in-plane thermal conductivities like earlier methods reported in literature. The approach was employed to study anisotropic thermal conductivity in alumina sheet, textured kaolin ceramics and montmorillonite. Since it is rare to find in-plane thermal conductivity values for suchmore » anisotropic thin samples in literature, this technique offers a useful variant to existing techniques.« less

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

PubMed

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

2018-05-09

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

Ionic Conductivity and Air Stability of Al-Doped Li₇La₃Zr₂O₁₂ Sintered in Alumina and Pt Crucibles.

PubMed

Xia, Wenhao; Xu, Biyi; Duan, Huanan; Guo, Yiping; Kang, Hongmei; Li, Hua; Liu, Hezhou

2016-03-02

Li7La3Zr2O12 (LLZO) is a promising electrolyte material for all-solid-state battery due to its high ionic conductivity and good stability with metallic lithium. In this article, we studied the effect of crucibles on the ionic conductivity and air stability by synthesizing 0.25Al doped LLZO pellets in Pt crucibles and alumina crucibles, respectively. The results show that the composition and microstructure of the pellets play important roles influencing the ionic conductivity, relative density, and air stability. Specifically, the 0.25Al-LLZO pellets sintered in Pt crucibles exhibit a high relative density (∼96%) and high ionic conductivity (4.48 × 10(-4) S cm(-1)). The ionic conductivity maintains 3.6 × 10(-4) S cm(-1) after 3-month air exposure. In contrast, the ionic conductivity of the pellets from alumina crucibles is about 1.81 × 10(-4) S cm(-1) and drops to 2.39 × 10(-5) S cm(-1) 3 months later. The large grains and the reduced grain boundaries in the pellets sintered in Pt crucibles are favorable to obtain high ionic conductivity and good air stability. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy results suggest that the formation of Li2CO3 on the pellet surface is probably another main reason, which is also closely related to the relative density and the amount of grain boundary within the pellets. This work stresses the importance of synthesis parameters, crucibles included, to obtain the LLZO electrolyte with high ionic conductivity and good air stability.

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Microemulsion based approach for nanospheres assembly into anisotropic nanostructures of NiMnO3 and their magnetic properties

NASA Astrophysics Data System (ADS)

Jha, Menaka; Kumar, Sandeep; Garg, Neha; Ramanujachary, Kandalam V.; Lofland, Samuel E.; Ganguli, Ashok K.

2018-02-01

The present study focuses on synthesis of anisotropic nanostructures of nickel manganese oxide (NiMnO3) obtained by thermal decomposition of nanocrystalline nickel manganese oxalate precursor, Ni0.5Mn0.5(C2O4)·2H2O which crystallized as nanorods. The synthesis of the oxalate precursor has been carried out via microemulsion-mediated process with cationic and non-ionic surfactants. The microemulsion led to reverse micelles, and the film flexibility of the micelle in presence of non-ionic surfactant (Tergitol) was reduced by increasing the chain length of the co-surfactant (1-butanol, 1-hexanol and 1-octanol) which led to the increase in reaction rate and hence increase in the aspect ratio of the nickel manganese oxalate by up to four times. However, in the presence of cationic surfactant, highly uniform nickel manganese oxalate nanorods were obtained. Further, the decomposition of the oxalate precursor was optimized to maintain the anisotropy of the rods of ternary metal oxide (NiMnO3). An electron microscopy study showed that the rods were made up of an assembly of ultrafine nanospheres. The NiMnO3 nanostructures were all ferrimagnetic with Curie temperature ranging between 437 and 467 K showing increasing saturation magnetization with increase in aspect ratio of the nanorods.

Electronic, optical properties and chemical bonding in six novel 1111-like chalcogenide fluorides AMChF (A=Sr, Ba; M=Cu, Ag; and Ch=S, Se, Te) from first principles calculations

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

Bannikov, V.V.; Shein, I.R.; Ivanovskii, A.L., E-mail: ivanovskii@ihim.uran.ru

2012-12-15

Employing first-principles band structure calculations, we have examined the electronic, optical properties and the peculiarities of the chemical bonding for six newly synthesized layered quaternary 1111-like chalcogenide fluorides SrAgSF, SrAgSeF, SrAgTeF, BaAgSF, BaAgSeF, and SrCuTeF, which are discussed in comparison with some isostructural 1111-like chalcogenide oxides. We found that all of the studied phases AMChF (A=Sr, Ba; M=Cu, Ag; and Ch=S, Se, Te) are semiconductors for which the fitted 'experimental' gaps lie in the interval from 2.23 eV (for SrAgSeF) to 3.07 eV (for SrCuTeF). The near-Fermi states of AMChF are formed exclusively by the valence orbitals of the atomsmore » from the blocks (MCh); thus, these phases belong to the layered materials with 'natural multiple quantum wells'. The bonding in these new AMChF phases is described as a high-anisotropic mixture of ionic and covalent contributions, where ionic M-Ch bonds together with covalent M-Ch and Ch-Ch bonds take place inside blocks (MCh), while inside blocks (AF) and between the adjacent blocks (MCh)/(AF) mainly ionic bonds emerge. - Graphical Abstract: Isoelectronic surface for SrAgSeF and atomic-resolved densities of states for SrAgTeF, and SrCuTeF. Highlights: Black-Right-Pointing-Pointer Very recently six new layered 1111-like chalcogenide fluorides AMChF were synthesized. Black-Right-Pointing-Pointer Electronic, optical properties for AMChF phases were examined from first principles. Black-Right-Pointing-Pointer All these materials are characterized as non-magnetic semiconductors. Black-Right-Pointing-Pointer Bonding is highly anisotropic and includes ionic and covalent contributions. Black-Right-Pointing-Pointer Introduction of magnetic ions in AMChF is proposed for search of novel magnetic materials.« less

A 23Na Multiple-Quantum-Filtered NMR Study of the Effect of the Cytoskeleton Conformation on the Anisotropic Motion of Sodium Ions in Red Blood Cells

NASA Astrophysics Data System (ADS)

Knubovets, Tatyana; Shinar, Hadassah; Eliav, Uzi; Navon, Gil

1996-01-01

Recently, it has been shown that23Na double-quantum-filtered NMR spectroscopy can be used to detect anisotropic motion of bound sodium ions in biological systems. The technique is based on the formation of the second-rank tensor when the quadrupolar interaction is not averaged to zero. Using this method, anisotropic motion of bound sodium in human and dog red blood cells was detected, and the effect was shown to depend on the integrity of the membrane cytoskeleton. In the present study, multiple-quantum-filtered techniques were applied in combination with a quadrupolar echo to measure the transverse-relaxation times,T2fandT2s. Line fitting was performed to obtain the values of the residual quadrupolar interaction, which was measured for sodium in a variety of mammalian erythrocytes of different size, shape, rheological properties, and sodium concentrations. Human unsealed white ghosts were used to study sodium bound at the anisotropic sites on the inner side of the RBC membrane. Modulations of the conformation of the cytoskeleton by the variation of either the ionic strength or pH of the suspending medium caused drastic changes in both the residual quadrupolar interaction andT2fdue to changes in the fraction of bound sodium ions as well as changes in the structure of the binding sites. By combining the two spectroscopic parameters, structural change can be followed. The changes in the structure of the sodium anisotropic binding sites deduced by this method were found to correlate with known conformational changes of the membrane cytoskeleton. Variations of the medium pH affected both the fraction of bound sodium ions and the structure of the anisotropic binding sites. Sodium and potassium were shown to bind to the anisotropic binding sites with the same affinity.

The role of electrostatics in protein-protein interactions of a monoclonal antibody.

PubMed

Roberts, D; Keeling, R; Tracka, M; van der Walle, C F; Uddin, S; Warwicker, J; Curtis, R

2014-07-07

Understanding how protein-protein interactions depend on the choice of buffer, salt, ionic strength, and pH is needed to have better control over protein solution behavior. Here, we have characterized the pH and ionic strength dependence of protein-protein interactions in terms of an interaction parameter kD obtained from dynamic light scattering and the osmotic second virial coefficient B22 measured by static light scattering. A simplified protein-protein interaction model based on a Baxter adhesive potential and an electric double layer force is used to separate out the contributions of longer-ranged electrostatic interactions from short-ranged attractive forces. The ionic strength dependence of protein-protein interactions for solutions at pH 6.5 and below can be accurately captured using a Deryaguin-Landau-Verwey-Overbeek (DLVO) potential to describe the double layer forces. In solutions at pH 9, attractive electrostatics occur over the ionic strength range of 5-275 mM. At intermediate pH values (7.25 to 8.5), there is a crossover effect characterized by a nonmonotonic ionic strength dependence of protein-protein interactions, which can be rationalized by the competing effects of long-ranged repulsive double layer forces at low ionic strength and a shorter ranged electrostatic attraction, which dominates above a critical ionic strength. The change of interactions from repulsive to attractive indicates a concomitant change in the angular dependence of protein-protein interaction from isotropic to anisotropic. In the second part of the paper, we show how the Baxter adhesive potential can be used to predict values of kD from fitting to B22 measurements, thus providing a molecular basis for the linear correlation between the two protein-protein interaction parameters.

Research Update: Fast and tunable nanoionics in vertically aligned nanostructured films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; MacManus-Driscoll, Judith L.

2017-04-01

This review provides the design principles to develop new nanoionic applications using vertically aligned nanostructured (VAN) thin films, incorporating two phases which self-assemble in one film. Tunable nanoionics has attracted great attention for energy and device applications, such as ion batteries, solid oxide fuel cells, catalysts, memories, and neuromorphic devices. Among many proposed device architectures, VAN films have strong potential for nanoionic applications since they show enhanced ionic conductivity and tunability. Here, we will review the recent progress on state-of-the-art nanoionic applications, which have been realized by using VAN films. In many VAN systems made by the inclusion of an oxygen ionic insulator, it is found that ions flow through the vertical heterointerfaces. The observation is consistent with structural incompatibility at the vertical heteroepitaxial interfaces resulting in oxygen deficiency in one of the phases and hence to oxygen ion conducting pathways. In other VAN systems where one of the phases is an ionic conductor, ions flow much faster within the ionic conducting phase than within the corresponding plain film. The improved ionic conduction coincides with much improved crystallinity in the ionically conducting nanocolumnar phase, induced by use of the VAN structure. Furthermore, for both cases Joule heating effects induced by localized ionic current flow also play a role for enhanced ionic conductivity. Nanocolumn stoichiometry and strain are other important parameters for tuning ionic conductivity in VAN films. Finally, double-layered VAN film architectures are discussed from the perspective of stabilizing VAN structures which would be less stable and hence less perfect when grown on standard substrates.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

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

DFT-based ab initio MD simulation of the ionic conduction in doped ZrO₂ systems under epitaxial strain.

PubMed

Oka, M; Kamisaka, H; Fukumura, T; Hasegawa, T

2015-11-21

The oxygen ionic conduction in ZrO2 systems under tensile epitaxial strain was investigated by performing ab initio molecular dynamics (MD) calculations based on density functional theory (DFT) to elucidate the essential factors in the colossal ionic conductivity observed in the yttria stabilized ZrO2 (YSZ)/SrTiO3 heterostructure. Three factors were evaluated: lattice strain, oxygen vacancies, and dopants. Phonon calculations based on density functional perturbation theory (DFPT) were used to obtain the most stable structure for nondoped ZrO2 under 7% tensile strain along the a- and b-axes. This structure has the space group Pbcn, which is entirely different from that of cubic ZrO2, suggesting that previous ab initio MD calculations assuming cubic ZrO2 may have overestimated the ionic conductivity due to relaxation from the initial structure to the stable structure (Pbcn). Our MD calculations revealed that the ionic conductivity is enhanced only when tensile strain and oxygen vacancies are incorporated, although the presently obtained diffusion constant is far below the range for the colossal ionic conduction experimentally observed. The enhanced ionic conductivity is due to the combined effects of oxygen sublattice formation induced by strain and deformation of this sublattice by oxygen vacancies.

Ultrahigh-throughput exfoliation of graphite into pristine ‘single-layer’ graphene using microwaves and molecularly engineered ionic liquids

NASA Astrophysics Data System (ADS)

Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

2015-09-01

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards ‘single-layer’ graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml-1, and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Experimental evaluation of electrical conductivity imaging of anisotropic brain tissues using a combination of diffusion tensor imaging and magnetic resonance electrical impedance tomography

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

Sajib, Saurav Z. K.; Jeong, Woo Chul; Oh, Tong In

Anisotropy of biological tissues is a low-frequency phenomenon that is associated with the function and structure of cell membranes. Imaging of anisotropic conductivity has potential for the analysis of interactions between electromagnetic fields and biological systems, such as the prediction of current pathways in electrical stimulation therapy. To improve application to the clinical environment, precise approaches are required to understand the exact responses inside the human body subjected to the stimulated currents. In this study, we experimentally evaluate the anisotropic conductivity tensor distribution of canine brain tissues, using a recently developed diffusion tensor-magnetic resonance electrical impedance tomography method. At lowmore » frequency, electrical conductivity of the biological tissues can be expressed as a product of the mobility and concentration of ions in the extracellular space. From diffusion tensor images of the brain, we can obtain directional information on diffusive movements of water molecules, which correspond to the mobility of ions. The position dependent scale factor, which provides information on ion concentration, was successfully calculated from the magnetic flux density, to obtain the equivalent conductivity tensor. By combining the information from both techniques, we can finally reconstruct the anisotropic conductivity tensor images of brain tissues. The reconstructed conductivity images better demonstrate the enhanced signal intensity in strongly anisotropic brain regions, compared with those resulting from previous methods using a global scale factor.« less

Fundamentals of ionic conductivity relaxation gained from study of procaine hydrochloride and procainamide hydrochloride at ambient and elevated pressure.

PubMed

Wojnarowska, Z; Swiety-Pospiech, A; Grzybowska, K; Hawelek, L; Paluch, M; Ngai, K L

2012-04-28

The pharmaceuticals, procaine hydrochloride and procainamide hydrochloride, are glass-forming as well as ionically conducting materials. We have made dielectric measurements at ambient and elevated pressures to characterize the dynamics of the ion conductivity relaxation in these pharmaceuticals, and calorimetric measurements for the structural relaxation. Perhaps due to their special chemical and physical structures, novel features are found in the ionic conductivity relaxation of these pharmaceuticals. Data of conductivity relaxation in most ionic conductors when represented by the electric loss modulus usually show a single resolved peak in the electric modulus loss M(")(f) spectra. However, in procaine hydrochloride and procainamide hydrochloride we find in addition another resolved loss peak at higher frequencies over a temperature range spanning across T(g). The situation is analogous to many non-ionic glass-formers showing the presence of the structural α-relaxation together with the Johari-Goldstein (JG) β-relaxation. Naturally the analogy leads us to name the slower and faster processes resolved in procaine hydrochloride and procainamide hydrochloride as the primary α-conductivity relaxation and the secondary β-conductivity relaxation, respectively. The analogy of the β-conductivity relaxation in procaine HCl and procainamide HCl with JG β-relaxation in non-ionic glass-formers goes further by the finding that the β-conductivity is strongly related to the α-conductivity relaxation at temperatures above and below T(g). At elevated pressure but compensated by raising temperature to maintain α-conductivity relaxation time constant, the data show invariance of the ratio between the β- and the α-conductivity relaxation times to changes of thermodynamic condition. This property indicates that the β-conductivity relaxation has fundamental importance and is indispensable as the precursor of the α-conductivity relaxation, analogous to the relation found between the Johari-Goldstein β-relaxation and the structural α-relaxation in non-ionic glass-forming systems. The novel features of the ionic conductivity relaxation are brought out by presenting the measurements in terms of the electric modulus or permittivity. If presented in terms of conductivity, the novel features are lost. This warns against insisting that a log-log plot of conductivity vs. frequency is optimal to reveal and interpret the dynamics of ionic conductors.

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

Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of freemore » ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.« less

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

NASA Astrophysics Data System (ADS)

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

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

Ionic conduction in sodium azide under high pressure: Experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Wang, Qinglin; Ma, Yanzhang; Sang, Dandan; Wang, Xiaoli; Liu, Cailong; Hu, Haiquan; Wang, Wenjun; Zhang, Bingyuan; Fan, Quli; Han, Yonghao; Gao, Chunxiao

2018-04-01

Alkali metal azides can be used as starting materials for the synthesis of polymeric nitrogen, a potential material of high energy density. In this letter, we report the ionic transport behavior in sodium azide under high pressure by in situ impedance spectroscopy and density functional theory calculations. The ionic transportation consists of ion transfer and Warburg diffusion processes. The ionic migration channels and barrier energy were given for the high-pressure phases. The enhanced ionic conductivity of the γ phase with pressure is because of the formation of space charge regions in the grain boundaries. This ionic conduction and grain boundary effect in NaN3 under pressures could shed light on the better understanding of the conduction mechanism of alkali azides and open up an area of research for polymeric nitrogen in these compounds and other high-energy-density polynitrides.

The phase diagram of high-pressure superionic ice

DOE PAGES

Sun, Jiming; Clark, Bryan K.; Torquato, Salvatore; ...

2015-08-28

Superionic ice is a special group of ice phases at high temperature and pressure, which may exist in ice-rich planets and exoplanets. In superionic ice liquid hydrogen coexists with a crystalline oxygen sublattice. At high pressures, the properties of superionic ice are largely unknown. Here we report evidence that from 280 GPa to 1.3 TPa, there are several competing phases within the close-packed oxygen sublattice. At even higher pressure, the close-packed structure of the oxygen sublattice becomes unstable to a new unusual superionic phase in which the oxygen sublattice takes the P2 1/c symmetry. We also discover that higher pressuremore » phases have lower transition temperatures. The diffusive hydrogen in the P2 1/c superionic phase shows strong anisotropic behaviour and forms a quasi-two-dimensional liquid. The ionic conductivity changes abruptly in the solid to close-packed superionic phase transition, but continuously in the solid to P2 1/c superionic phase transition.« less

Comparative study of perovskite-type scintillator materials CsCaI3 and KCaI3 via first-principles calculations

NASA Astrophysics Data System (ADS)

Kang, Byungkyun; Feng, Qingguo; Biswas, Koushik

2018-02-01

Several members of a large family of perovskite-like halides with a common chemical formula, ABX3 (A  =  monovalent, B  =  divalent, and X  =  halogen ion), are being investigated for their interesting properties and potential technological applications. CsCaI3 and KCaI3 are two such ionic compounds who are of interest in the quest for superior and cost-effective alternatives to NaI or CsI based scintillators. They are the subject of this first-principles based computational study. Both are wide-gap materials having primarily I 5p and Ca 3d characters near the valence and conduction band edges, respectively. Although built from [CaI6] octahedral motifs, structural differences between the two compounds is reflected in anisotropic electron effective mass and distinctive formation and migration of self-trapped holes. We discuss these properties as they relate to scintillation decay and proportional light yield.

Atomistic modeling of La3+ doping segregation effect on nanocrystalline yttria-stabilized zirconia.

PubMed

Zhang, Shenli; Sha, Haoyan; Castro, Ricardo H R; Faller, Roland

2018-05-16

The effect of La3+ doping on the structure and ionic conductivity change in nanocrystalline yttria-stabilized zirconia (YSZ) was studied using a combination of Monte Carlo and molecular dynamics simulations. The simulation revealed the segregation of La3+ at eight tilt grain boundary (GB) structures and predicted an average grain boundary (GB) energy decrease of 0.25 J m-2, which is close to the experimental values reported in the literature. Cation stabilization was found to be the main reason for the GB energy decrease, and energy fluctuations near the grain boundary are smoothed out with La3+ segregation. Both dynamic and energetic analysis on the Σ13(510)/[001] GB structure revealed La3+ doping hinders O2- diffusion in the GB region, where the diffusion coefficient monotonically decreases with increasing La3+ doping concentration. The effect was attributed to the increase in the site-dependent migration barriers for O2- hopping caused by segregated La3+, which also leads to anisotropic diffusion at the GB.

Anomalous frequency-dependent ionic conductivity of lesion-laden human-brain tissue

NASA Astrophysics Data System (ADS)

Emin, David; Akhtari, Massoud; Fallah, Aria; Vinters, Harry V.; Mathern, Gary W.

2017-10-01

We study the effect of lesions on our four-electrode measurements of the ionic conductivity of (˜1 cm3) samples of human brain excised from patients undergoing pediatric epilepsy surgery. For most (˜94%) samples, the low-frequency ionic conductivity rises upon increasing the applied frequency. We attributed this behavior to the long-range (˜0.4 mm) diffusion of solvated sodium cations before encountering intrinsic impenetrable blockages such as cell membranes, blood vessels, and cell walls. By contrast, the low-frequency ionic conductivity of some (˜6%) brain-tissue samples falls with increasing applied frequency. We attribute this unusual frequency-dependence to the electric-field induced liberation of sodium cations from traps introduced by the unusually severe pathology observed in samples from these patients. Thus, the anomalous frequency-dependence of the ionic conductivity indicates trap-producing brain lesions.

Generalized analytic solutions and response characteristics of magnetotelluric fields on anisotropic infinite faults

NASA Astrophysics Data System (ADS)

Bing, Xue; Yicai, Ji

2018-06-01

In order to understand directly and analyze accurately the detected magnetotelluric (MT) data on anisotropic infinite faults, two-dimensional partial differential equations of MT fields are used to establish a model of anisotropic infinite faults using the Fourier transform method. A multi-fault model is developed to expand the one-fault model. The transverse electric mode and transverse magnetic mode analytic solutions are derived using two-infinite-fault models. The infinite integral terms of the quasi-analytic solutions are discussed. The dual-fault model is computed using the finite element method to verify the correctness of the solutions. The MT responses of isotropic and anisotropic media are calculated to analyze the response functions by different anisotropic conductivity structures. The thickness and conductivity of the media, influencing MT responses, are discussed. The analytic principles are also given. The analysis results are significant to how MT responses are perceived and to the data interpretation of the complex anisotropic infinite faults.

Strong anisotropic optical conductivity in two-dimensional puckered structures: The role of the Rashba effect

NASA Astrophysics Data System (ADS)

Saberi-Pouya, S.; Vazifehshenas, T.; Salavati-fard, T.; Farmanbar, M.; Peeters, F. M.

2017-08-01

We calculate the optical conductivity of an anisotropic two-dimensional system with Rashba spin-flip excitation within the Kubo formalism. We show that the anisotropic Rashba effect caused by an external field significantly changes the magnitude of the spin splitting. Furthermore, we obtain an analytical expression for the longitudinal optical conductivity associated with interband transitions as a function of the frequency for arbitrary polarization angle. We find that the diagonal components of the optical conductivity tensor are direction dependent and the optical absorption spectrum exhibits a strongly anisotropic absorption window. The height and width of this absorption window are very sensitive to the anisotropy of the system. While the height of absorption peak increases with increasing effective mass anisotropy ratio, the peak intensity is larger when the light polarization is along the armchair direction. Moreover, the absorption peak width becomes broader as the density-of-states mass or Rashba interaction is enhanced. These features in the optical absorption spectrum can be used to determine parameters relevant for spintronics.

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

PubMed Central

Zhang, Ruisi; Chen, Yuanfen; Montazami, Reza

2015-01-01

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

Enhancement of the ionic conductivity of olivine by the water incorporation based on the Mg diffusivity

NASA Astrophysics Data System (ADS)

Katsura, T.; Fei, H.; Koizumi, S.; Sakamoto, N.; Yurimoto, H.

2016-12-01

Although the water corporation has been considered to enhance the electrical conductivity of olivine by the proton conduction, the magnitude of the proton conduction is relatively small at asthenospheric temperatures because of its smaller activation energy than those of the small polaron and ionic conductions. However, the water incorporation could enhance the ionic conduction, because it should increase the defect density in the Mg sites. Since the ionic conductivity is proportional to the diffusivity, we have measured the self-diffusion coefficients of Mg in forsterite as a function of pressure, temperature and water content. We annealed fine-grained polycrystalline aggregates of forsterite with water contents up to 300 ppm, on whose polished plane a 25Mg-enriched Mg2SiO4 thin film was made, at pressures of 1 to 13 GPa and temperatures of 1100 to 1300 K. The lattice and grain-boundary diffusion coefficients were calculated simultaneously using profiles obtained by the depth analysis of SIMS. Experimental results gave the activation energy of 280 ± 30 and 360 ± 30 kJ/mol, activation volumes of 4.3 ± 0.3 and 3.9 ± 0.7 cm3/mol, and water content exponents of 1.2 ± 0.2 and 1.0 ± 0.1 for the lattice and grain-boundary diffusions, respectively. Using the ionic conduction data by Constable [2006] and Yoshino et al. [2009], and the water and pressure effects on Mg diffusivity in this study, the ionic conduction is found by 2 orders of magnitude higher than the small polaron and proton conductions under oceanic-asthenosphere conditions. Thus, the high conductivity of the oceanic asthenosphere will be governed by the water-enhanced ionic conduction. The negative pressure dependence of the Mg diffusivity and the gradual temperature increase in the asthenosphere will produce a conductivity maximum at the top of the asthenosphere. The high-conductivity layer at the top of the asthenosphere observed under very young oceanic plates can be attributed to this ionic conduction maximum.

Aligning Ag Nanowires by a Facile Bioinspired Directional Liquid Transfer: Toward Anisotropic Flexible Conductive Electrodes.

PubMed

Meng, Lili; Bian, Ruixin; Guo, Cheng; Xu, Bojie; Liu, Huan; Jiang, Lei

2018-06-01

Recent years have witnessed the booming development of transparent flexible electrodes (TFEs) for their applications in electronics and optoelectronic devices. Various strategies have thus been developed for preparing TFEs with higher flexibility and conductivity. However, little work has focused on TFEs with anisotropic conductivity. Here, a facile strategy of directional liquid transfer is proposed, guided by a conical fibers array (CFA), based on which silver nanowires (AgNWs) are aligned on a soft poly(ethylene terephthalate) substrate in large scale. After further coating a second thin layer of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), a TFE with notable anisotropic conductivity and excellent optical transmittance of 95.2% is prepared. It is proposed that the CFA enables fine control over the receding of the three-phase contact line during the dewetting process, where AgNWs are guided and aligned by the as-generated directional stress. Moreover, anisotropic electrochemical deposition is enabled where the Cu nanoparticles deposit only on the oriented AgNWs, leading to a surface with anisotropic wetting behavior. Importantly, the approach enables alignment of AgNWs via multiple directions at one step. It is envisioned that the as-developed approach will provide an optional approach for simple and low-cost preparation of TFE with various functions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite mixed oxide ionic and electronic conductors for hydrogen separation

DOEpatents

Gopalan, Srikanth [Westborough, MA; Pal, Uday B [Dover, MA; Karthikeyan, Annamalai [Quincy, MA; Hengdong, Cui [Allston, MA

2009-09-15

A mixed ionic and electronic conducting membrane includes a two-phase solid state ceramic composite, wherein the first phase comprises an oxygen ion conductor and the second phase comprises an n-type electronically conductive oxide, wherein the electronically conductive oxide is stable at an oxygen partial pressure as low as 10.sup.-20 atm and has an electronic conductivity of at least 1 S/cm. A hydrogen separation system and related methods using the mixed ionic and electronic conducting membrane are described.

Effects of impurity doping on ionic conductivity and polarization phenomenon in TlBr

NASA Astrophysics Data System (ADS)

Du, Mao-Hua

2013-02-01

Ionic conductivity due to vacancy diffusion and the resulting polarization phenomenon are major challenges to the development of TlBr radiation detector. It had been proposed that impurity doping of TlBr can suppress the ionic conductivity because the impurities can getter vacancies to form neutral complexes. This paper shows that the isolated vacancies can maintain their equilibrium concentrations even at room temperature, rendering any gettering methods ineffective. The main effect of doping is to change the Fermi level and consequently the vacancy concentration. The minimal ionic conductivity is reached at the donor concentration of [D+] = 4 × 1016 cm-3.

Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution.

PubMed

Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

2016-05-19

Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room-Temperature Ionic Liquids. 1. Variation of Anionic Species.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2015-12-03

A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications.

Local Structural Investigations, Defect Formation, and Ionic Conductivity of the Lithium Ionic Conductor Li 4 P 2 S 6

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

Dietrich, Christian; Sadowski, Marcel; Sicolo, Sabrina

Glassy, glass–ceramic, and crystalline lithium thiophosphates have attracted interest in their use as solid electrolytes in all-solid-state batteries. Despite similar structural motifs, including PS 4 3–, P 2S 6 4–, and P 2S 7 4– polyhedra, these materials exhibit a wide range of possible compositions, crystal structures, and ionic conductivities. Here, we present a combined approach of Bragg diffraction, pair distribution function analysis, Raman spectroscopy, and 31P magic angle spinning nuclear magnetic resonance spectroscopy to study the underlying crystal structure of Li 4P 2S 6. In this work, we show that the material crystallizes in a planar structural arrangement asmore » a glass ceramic composite, explaining the observed relatively low ionic conductivity, depending on the fraction of glass content. Calculations based on density functional theory provide an understanding of occurring diffusion pathways and ionic conductivity of this Li + ionic conductor.« less

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

Study on the temperature-dependent coupling among viscosity, conductivity and structural relaxation of ionic liquids.

PubMed

Yamaguchi, Tsuyoshi; Yonezawa, Takuya; Koda, Shinobu

2015-07-15

The frequency-dependent viscosity and conductivity of three imidazolium-based ionic liquids were measured at several temperatures in the MHz region, and the results are compared with the intermediate scattering functions determined by neutron spin echo spectroscopy. The relaxations of both the conductivity and the viscosity agree with that of the intermediate scattering function at the ionic correlation when the relaxation time is short. As the relaxation time increases, the relaxations of the two transport properties deviate to lower frequencies than that of the ionic structure. The deviation begins at a shorter relaxation time for viscosity than for conductivity, which explains the fractional Walden rule between the zero-frequency values of the shear viscosity and the molar conductivity.

Enhancing the Ion Transport in LiMn1.5Ni0.5O4 by Altering the Particle Wulff Shape via Anisotropic Surface Segregation.

PubMed

Huang, Jiajia; Liu, Haodong; Zhou, Naixie; An, Ke; Meng, Ying Shirley; Luo, Jian

2017-10-25

Spontaneous and anisotropic surface segregation of W cations in LiMn 1.5 Ni 0.5 O 4 particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by ∼5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn 3+ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. This is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn 1.5 Ni 0.5 O 4 spinel materials.

3D anisotropic modeling and identification for airborne EM systems based on the spectral-element method

NASA Astrophysics Data System (ADS)

Huang, Xin; Yin, Chang-Chun; Cao, Xiao-Yue; Liu, Yun-He; Zhang, Bo; Cai, Jing

2017-09-01

The airborne electromagnetic (AEM) method has a high sampling rate and survey flexibility. However, traditional numerical modeling approaches must use high-resolution physical grids to guarantee modeling accuracy, especially for complex geological structures such as anisotropic earth. This can lead to huge computational costs. To solve this problem, we propose a spectral-element (SE) method for 3D AEM anisotropic modeling, which combines the advantages of spectral and finite-element methods. Thus, the SE method has accuracy as high as that of the spectral method and the ability to model complex geology inherited from the finite-element method. The SE method can improve the modeling accuracy within discrete grids and reduce the dependence of modeling results on the grids. This helps achieve high-accuracy anisotropic AEM modeling. We first introduced a rotating tensor of anisotropic conductivity to Maxwell's equations and described the electrical field via SE basis functions based on GLL interpolation polynomials. We used the Galerkin weighted residual method to establish the linear equation system for the SE method, and we took a vertical magnetic dipole as the transmission source for our AEM modeling. We then applied fourth-order SE calculations with coarse physical grids to check the accuracy of our modeling results against a 1D semi-analytical solution for an anisotropic half-space model and verified the high accuracy of the SE. Moreover, we conducted AEM modeling for different anisotropic 3D abnormal bodies using two physical grid scales and three orders of SE to obtain the convergence conditions for different anisotropic abnormal bodies. Finally, we studied the identification of anisotropy for single anisotropic abnormal bodies, anisotropic surrounding rock, and single anisotropic abnormal body embedded in an anisotropic surrounding rock. This approach will play a key role in the inversion and interpretation of AEM data collected in regions with anisotropic geology.

Two-relaxation-time lattice Boltzmann method for the anisotropic dispersive Henry problem

NASA Astrophysics Data System (ADS)

Servan-Camas, Borja; Tsai, Frank T.-C.

2010-02-01

This study develops a lattice Boltzmann method (LBM) with a two-relaxation-time collision operator (TRT) to cope with anisotropic heterogeneous hydraulic conductivity and anisotropic velocity-dependent hydrodynamic dispersion in the saltwater intrusion problem. The directional-speed-of-sound technique is further developed to address anisotropic hydraulic conductivity and dispersion tensors. Forcing terms are introduced in the LBM to correct numerical errors that arise during the recovery procedure and to describe the sink/source terms in the flow and transport equations. In order to facilitate the LBM implementation, the forcing terms are combined with the equilibrium distribution functions (EDFs) to create pseudo-EDFs. This study performs linear stability analysis and derives LBM stability domains to solve the anisotropic advection-dispersion equation. The stability domains are used to select the time step at which the lattice Boltzmann method provides stable solutions to the numerical examples. The LBM was implemented for the anisotropic dispersive Henry problem with high ratios of longitudinal to transverse dispersivities, and the results compared well to the solutions in the work of Abarca et al. (2007).

Insulated Conducting Cantilevered Nanotips and Two-Chamber Recording System for High Resolution Ion Sensing AFM

PubMed Central

Meckes, Brian; Arce, Fernando Teran; Connelly, Laura S.; Lal, Ratnesh

2014-01-01

Biological membranes contain ion channels, which are nanoscale pores allowing controlled ionic transport and mediating key biological functions underlying normal/abnormal living. Synthetic membranes with defined pores are being developed to control various processes, including filtration of pollutants, charge transport for energy storage, and separation of fluids and molecules. Although ionic transport (currents) can be measured with single channel resolution, imaging their structure and ionic currents simultaneously is difficult. Atomic force microscopy enables high resolution imaging of nanoscale structures and can be modified to measure ionic currents simultaneously. Moreover, the ionic currents can also be used to image structures. A simple method for fabricating conducting AFM cantilevers to image pore structures at high resolution is reported. Tungsten microwires with nanoscale tips are insulated except at the apex. This allows simultaneous imaging via cantilever deflections in normal AFM force feedback mode as well as measuring localized ionic currents. These novel probes measure ionic currents as small as picoampere while providing nanoscale spatial resolution surface topography and is suitable for measuring ionic currents and conductance of biological ion channels. PMID:24663394

Elucidating the correlation between morphology and ion dynamics in polymerized ionic liquids.

NASA Astrophysics Data System (ADS)

Heres, Maximilian; Cosby, Tyler; Iacob, Ciprian; Runt, James; Benson, Roberto; Liu, Hongjun; Paddison, Stephen; Sangoro, Joshua

Charge transport and dynamics are investigated for a series of poly-ammonium and poly-imidazolium-based polymerized ionic liquids (polyIL) with a common bis(trifluoromethylsulfonyl)imide anion using broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry. A significant enhancement of the Tg independent ionic conductivity is observed for ammonium based polyIL with shorter pendant groups, in comparison to imidazolium based systems. These results emphasize the importance of polymer backbone spacing as well as counter-ion size on ionic conductivity in polymerized ionic liquids. NSF DMR 1508394.

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

PubMed

Kim, Jaehwan; Bae, Seok-Hu; Kotal, Moumita; Stalbaum, Tyler; Kim, Kwang J; Oh, Il-Kwon

2017-08-01

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m -1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

PubMed

Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

2014-02-12

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Anisotropic in-plane thermal conductivity observed in few-layer black phosphorus

PubMed Central

Luo, Zhe; Maassen, Jesse; Deng, Yexin; Du, Yuchen; Garrelts, Richard P.; Lundstrom, Mark S; Ye, Peide D.; Xu, Xianfan

2015-01-01

Black phosphorus has been revisited recently as a new two-dimensional material showing potential applications in electronics and optoelectronics. Here we report the anisotropic in-plane thermal conductivity of suspended few-layer black phosphorus measured by micro-Raman spectroscopy. The armchair and zigzag thermal conductivities are ∼20 and ∼40 W m−1 K−1 for black phosphorus films thicker than 15 nm, respectively, and decrease to ∼10 and ∼20 W m−1 K−1 as the film thickness is reduced, exhibiting significant anisotropy. The thermal conductivity anisotropic ratio is found to be ∼2 for thick black phosphorus films and drops to ∼1.5 for the thinnest 9.5-nm-thick film. Theoretical modelling reveals that the observed anisotropy is primarily related to the anisotropic phonon dispersion, whereas the intrinsic phonon scattering rates are found to be similar along the armchair and zigzag directions. Surface scattering in the black phosphorus films is shown to strongly suppress the contribution of long mean-free-path acoustic phonons. PMID:26472191

Ionic Liquid as an Effective Additive for Rechargeable Magnesium Batteries

DOE PAGES

Pan, Baofei; Lau, Ka -Cheong; Vaughey, John T.; ...

2017-03-02

Here, the effect of the addition of an ionic liquid DEME•TFSI to an electrolyte solution of Mg(HMDS) 2-MgCl 2 in THF was studied electrochemically and spectroscopically. Reversible magnesium deposition/dissolution was achieved with the DEME•TFSI-modified electrolyte. This electrolyte shows higher ionic conductivity, and a linear relationship was observed between the ionic conductivity and the concentration of DEME•TFSI in THF solution of Mg(HMDS) 2-MgCl 2. Mg-Mo 6S 8 coin cells have also been successfully cycled using Mg(HMDS) 2-MgCl 2 electrolyte with the addition of DEME•TFSI. Raman and NMR spectroscopy suggest that DEME•TFSI facilitates magnesium deposition/dissolution by improving ionic conductivity of the electrolyte.

Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution

PubMed Central

Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

2016-01-01

Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances. PMID:27193448

Scaling effects in sodium zirconium silicate phosphate (Na 1+ xZr 2Si xP 3- xO 12) ion-conducting thin films

DOE PAGES

Ihlefeld, Jon F.; Gurniak, Emily; Jones, Brad H.; ...

2016-05-04

Preparation of sodium zirconium silicate phosphate (NaSICon), Na 1+xZr 2Si xP 3–xO 12 (0.25 ≤ x ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an x = 0.25 composition at 2.3 × 10 –5 S/cm. In conclusion, themore » decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.« less

Synthesis of new solid polymer electrolyte and actuator based on PEDOT/NBR/ionic liquid

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2006-03-01

The conducting polymer actuator was presented. The solid polymer electrolyte based on nitrile rubber (NBR) activated with different ionic liquids was prepared. The three different grades of NBR films were synthesized by emulsion polymerization with different amount of acrylonitrile, 23, 35, and 40 mol. %, respectively. The effect of acrylonitrile content on the ionic conductivity and dielectric constant of solid polymer electrolytes was characterized. A conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique, and room temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X [where X= BF 4 -, PF 6 -, (CF 3SO II) IIN -], were absorbed into the composite film. The effects of the anion size of the ionic liquids on the displacement of the actuator were examined. The displacement increased with increasing the anion-size of the ionic liquids.

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

PubMed

Zhang, Xiaokun; Xie, Jin; Shi, Feifei; Lin, Dingchang; Liu, Yayuan; Liu, Wei; Pei, Allen; Gong, Yongji; Wang, Hongxia; Liu, Kai; Xiang, Yong; Cui, Yi

2018-06-13

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li + transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10 -3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10 -4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

2016-05-01

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

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

Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com

2016-05-06

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governedmore » by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.« less

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition.

PubMed

Shiotani, Shinya; Ohara, Koji; Tsukasaki, Hirofumi; Mori, Shigeo; Kanno, Ryoji

2017-08-01

In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li 7 P 3 S 11 : 70Li 2 S-30P 2 S 5 ). We found that the ionic conductivity of 75Li 2 S-25P 2 S 5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li 2 S-25P 2 S 5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

Local fields and effective conductivity tensor of ellipsoidal particle composite with anisotropic constituents

NASA Astrophysics Data System (ADS)

Kushch, Volodymyr I.; Sevostianov, Igor; Giraud, Albert

2017-11-01

An accurate semi-analytical solution of the conductivity problem for a composite with anisotropic matrix and arbitrarily oriented anisotropic ellipsoidal inhomogeneities has been obtained. The developed approach combines the superposition principle with the multipole expansion of perturbation fields of inhomogeneities in terms of ellipsoidal harmonics and reduces the boundary value problem to an infinite system of linear algebraic equations for the induced multipole moments of inhomogeneities. A complete full-field solution is obtained for the multi-particle models comprising inhomogeneities of diverse shape, size, orientation and properties which enables an adequate account for the microstructure parameters. The solution is valid for the general-type anisotropy of constituents and arbitrary orientation of the orthotropy axes. The effective conductivity tensor of the particulate composite with anisotropic constituents is evaluated in the framework of the generalized Maxwell homogenization scheme. Application of the developed method to composites with imperfect ellipsoidal interfaces is straightforward. Their incorporation yields probably the most general model of a composite that may be considered in the framework of analytical approach.

Imaging of isotropic and anisotropic conductivities from power densities in three dimensions

NASA Astrophysics Data System (ADS)

Monard, François; Rim, Donsub

2018-07-01

We present numerical reconstructions of anisotropic conductivity tensors in three dimensions, from knowledge of a finite family of power density functionals. Such a problem arises in the coupled-physics imaging modality ultrasound modulated electrical impedance tomography for instance. We improve on the algorithms previously derived in Bal et al (2013 Inverse Problems Imaging 7 353–75) Monard and Bal (2013 Commun. PDE 38 1183–207) for both isotropic and anisotropic cases, and we address the well-known issue of vanishing determinants in particular. The algorithm is implemented and we provide numerical results that illustrate the improvements.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Ion-mediated enhancement of xylem hydraulic conductivity in four Acer species: relationships with ecological and anatomical features.

PubMed

Nardini, Andrea; Dimasi, Federica; Klepsch, Matthias; Jansen, Steven

2012-12-01

The 'ionic effect', i.e., changes in xylem hydraulic conductivity (k(xyl)) due to variation of the ionic sap composition in vessels, was studied in four Acer species growing in contrasting environments differing in water availability. Hydraulic measurements of the ionic effect were performed together with measurements on the sap electrical conductivity, leaf water potential and vessel anatomy. The low ionic effect recorded in Acer pseudoplatanus L. and Acer campestre L. (15.8 and 14.7%, respectively), which represented two species from shady and humid habitats, was associated with a low vessel grouping index, high sap electrical conductivity and least negative leaf water potential. Opposite traits were found for Acer monspessulanum L. and Acer platanoides L., which showed an ionic effect of 23.6 and 23.1%, respectively, and represent species adapted to higher irradiance and/or lower water availability. These findings from closely related species provide additional support that the ionic effect could function as a compensation mechanism for embolism-induced loss of k(xyl), either as a result of high evaporative demand or increased risk of hydraulic failure.

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Lithium Fast-Ion Conductors: Polymer Based Materials.

DTIC Science & Technology

1987-05-30

significant ambient temperature ionic conductivities. Some of the -aterials may be of interest in other contexts. A study of lithium tetra...This work was a search for lithium-containing materials with ambient temperature ionic conductivities of 10- 5 (ohm-cm) " or larger. The work began with...1-8). The discovery of solids, e.g., sodium.8-alumina(l), and polymer-salt complexes, e.g., (PEO) 8 LiCIO 4 (3), with ionic conductivities approaching

Communication: Dimensionality of the ionic conduction pathways in glass and the mixed-alkali effect.

PubMed

Novy, Melissa; Avila-Paredes, Hugo; Kim, Sangtae; Sen, Sabyasachi

2015-12-28

A revised empirical relationship between the power law exponent of ac conductivity dispersion and the dimensionality of the ionic conduction pathway is established on the basis of electrical impedance spectroscopic (EIS) measurements on crystalline ionic conductors. These results imply that the "universal" ac conductivity dispersion observed in glassy solids is associated with ionic transport along fractal pathways. EIS measurements on single-alkali glasses indicate that the dimensionality of this pathway D is ∼2.5, while in mixed-alkali glasses, D is lower and goes through a minimum value of ∼2.2 when the concentrations of the two alkalis become equal. D and σ display similar variation with alkali composition, thus suggesting a topological origin of the mixed-alkali effect.

Fourth order discretization of anisotropic heat conduction operator

NASA Astrophysics Data System (ADS)

Krasheninnikova, Natalia; Chacon, Luis

2008-11-01

In magnetized plasmas, heat conduction plays an important role in such processes as energy confinement, turbulence, and a number of instabilities. As a consequence of the presence of a magnetic field, heat transport is strongly anisotropic, with energy flowing preferentially along the magnetic field direction. This in turn results in parallel and perpendicular heat conduction coefficients being separated by orders of magnitude. The computational difficulties in treating such heat conduction anisotropies are significant, as perpendicular dynamics numerically is polluted by the parallel one. In this work, we report on progress of the implementation of a fourth order, conservative finite volume discretization scheme for the anisotropic heat conduction operator into the extended MHD code PIXIE3D [1]. We will demonstrate its spatial discretization accuracy and its effectiveness with two physical applications of interest, both of which feature a strong sensitivity to the heat conduction anisotropy: the thermal instability and the neoclassical tearing mode. [1] L. Chacon Phys. Plasmas 15, 056103 (2008)

Enhancing grain boundary ionic conductivity in mixed ionic-electronic conductors.

PubMed

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-04-10

Mixed ionic-electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2-δ-CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2-δ-Ce0.8Gd0.2O2-δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic-electronic conductor composites through processing induced modifications of the grain boundary defect distribution.

Influence of Electrical and Ionic Conductivities of Organic Electronic Ion Pump on Acetylcholine Exchange Performance

PubMed Central

Abdullayeva, Nazrin; Sankir, Mehmet

2017-01-01

By using an easy and effective method of depositing conjugated polymers (PEDOT:PSS) on flexible substrates, a new design for organic bioelectronic devices has been developed. The purpose was to build up a system that mimics the motion of neurotransmitters in the synaptic cleft by obtaining an electrical to chemical signal transport. Fourier transform infrared (FTIR) spectroscopy and Raman measurements have demonstrated that electrochemical overoxidation region which separates the pristine PEDOT:PSS electrodes and allows ionic conduction has been achieved successfully. The influence of both electrical and ionic conductivities on organic electronic ion pump (OEIP) performances has been studied. The ultimate goal was to achieve the highest equilibrium current density at the lowest applied voltage via enhancing the electrical conductivity of PEDOT:PSS and ionic conductivity of electrochemically overoxidized region. The highest equilibrium current density, which corresponds to 4.81 × 1017 number of ions of acetylcholine was about 41 μA cm−2 observed for the OEIP with the electrical conductivities of 54 S cm−1. This was a threshold electrical conductivity beyond which the OEIP performances were not changed much. Once Nafion™ has been applied for enhancing the ionic conductivity, the equilibrium current density increased about ten times and reached up to 408 μA cm−2. Therefore, it has been demonstrated that the OEIP performance mainly scales with the ionic conductivity. A straightforward method of producing organic bioelectronics is proposed here may provide a clue for their effortless mass production in the near future. PMID:28772946

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

Effects of anisotropic thermal conduction on wind properties in hot accretion flow

NASA Astrophysics Data System (ADS)

Bu, De-Fu; Wu, Mao-Chun; Yuan, Ye-Fei

2016-06-01

Previous works have clearly shown the existence of winds from black hole hot accretion flow and investigated their detailed properties. In extremely low accretion rate systems, the collisional mean-free path of electrons is large compared with the length-scale of the system, thus thermal conduction is dynamically important. When the magnetic field is present, the thermal conduction is anisotropic and energy transport is along magnetic field lines. In this paper, we study the effects of anisotropic thermal conduction on the wind production in hot accretion flows by performing two-dimensional magnetohydrodynamic simulations. We find that thermal conduction has only moderate effects on the mass flux of wind. But the energy flux of wind can be increased by a factor of ˜10 due to the increase of wind velocity when thermal conduction is included. The increase of wind velocity is because of the increase of driving forces (e.g. gas pressure gradient force and centrifugal force) when thermal conduction is included. This result demonstrates that thermal conduction plays an important role in determining the properties of wind.

Anisotropic interaction and stereoreactivity in a chemi-ionization process of OCS by collision with He*(2(3)S) metastable atoms.

PubMed

Horio, Takuya; Maeda, Satoshi; Kishimoto, Naoki; Ohno, Koichi

2006-09-28

Ionic-state-resolved collision energy dependence of Penning ionization cross sections for OCS with He*(2(3)S) metastable atoms was measured in a wide collision energy range from 20 to 350 meV. Anisotropic interaction potential for the OCS-He*(2(3)S) system was obtained by comparison of the experimental data with classical trajectory simulations. It has been found that attractive potential wells around the O and S atoms are clearly different in their directions. Around the O atom, the collinear approach is preferred (the well depth is ca. 90 meV), while the perpendicular approach is favored around the S atom (the well depth is ca. 40 meV). On the basis of the optimized potential energy surface and theoretical simulations, stereo reactivity around the O and S atoms was also investigated. The results were discussed in terms of anisotropy of the potential energy surface and the electron density distribution of molecular orbitals to be ionized.

High-fidelity Characterization on Anisotropic Thermal Conductivity of Carbon Nanotube Sheets and on their effects of Thermal Enhancement of Nanocomposites.

PubMed

Zhang, Xiao; Tan, Wei; Smail, Fiona; De Volder, Michael; Fleck, Norman; Boies, Adam

2018-06-19

Some assemblies of nanomaterials, like carbon nanotube (CNT) sheet or film, always show outstanding and anisotropic thermal properties. However, there is still a lack of comprehensive thermal conductivity (κ) characterizations on CNT sheets, as well as lack of estimations of their true contributions on thermal enhancement of polymer composites when used as additives. Always, these characterizations were hindered by the low heat capacity, anisotropic thermal properties or low electrical conductivity of assemblies and their nanocomposites. And the transient κ measurement and calculations were also hampered by accurate determination of parameters, like specific heat capacity, density and cross-section, which could be difficult and controversial for nanomaterials, like CNT sheets. Here, to measure anisotropic κ of CNT sheets directly with high fidelity, we modified the conventional steady-state method by measuring under vacuum and by infrared camera, and then comparing temperature profiles on both reference standard material and a CNT sheet sample. The highly anisotropic thermal conductivities of CNT sheets were characterized comprehensively, with κ/ρ in alignment direction as ~95 mW·m^2/(K·kg). Furthermore, by comparing the measured thermal properties of different CNT-epoxy resin composites, the heat conduction pathway created by the CNT hierarchical network was demonstrated to remain intact after the in-situ polymerization and curing process. The reliable and direct κ measurement rituals used here, dedicated to nanomaterials, will be also essential to assist in assemblies' application to heat dissipation and composite thermal enhancement. © 2018 IOP Publishing Ltd.

Pressure and temperature dependences of the ionic conductivities of the thallous halidesTlCl, TlBr, and TlI

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

Samara, G.A.

1981-01-15

Detailed studies of the pressure and temperature dependences of the ionic conductivities of TlCl and TlBr have allowed determination of the lattice volume relaxations and energies associated with the formation and motion of Schottky defects in these crystals. The volume relaxations deduced from the conductivity are found to be comparable in magnitude with values calculated from the strain energy model and a dynamical model. The association energy of Tl/sup +/ vacancies and divalent impurities was also determined for TlBr. A particularly important result is the finding that for these CsCl-type crystals the relaxation of the lattice associated with vacancy formationmore » is outward. Earlier studies on ionic crystals having the NaCl structure have yielded a similar result. This outward relaxation thus appears to be a general result for ionic crystals of both the NaCl and CsCl types (and possibly other ionic lattice types), in disagreement with earlier theoretical calculations which show that the relaxation should be inward for all models of ionic vacancies investigated. The conductivity of TlI was studied in both the (low temperature and pressure) orthorhombic phase as well as in the cubic CsCl-type phase. There is a large electronic contribution to the conductivity in the orthorhombic phase. An interesting result for all three materials is the observation in the cubic phase of a pressure-induced transition from ionic to electronic conduction. This is in qualitative agreement with what is known about the pressure dependences of the electronic structure of these materials.« less

Response surface method (RSM) for optimization of ionic conductivity of membranes polymer electrolyte poly (vinylidene fluoride) (PVDF) with polyvinyl pyrrolidone (PVP) as pore forming agent

NASA Astrophysics Data System (ADS)

Dyartanti, E. R.; Susanto, H.; Widiasa, I. N.; Purwanto, A.

2017-06-01

The Membranes Polymer Gel Electrolyte (MPGEs) based poly (vinylidene fluoride) (PVDF) was prepared by a phase inversion method using polyvinyl pyrrolidone (PVP) as a pore-forming agent and N, N-dimethyl acetamide (DMAc) as a solvent and water as non solvet. The membranes were then soaked in 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC) / dimethyl carbonate (DMC) / Diethyl carbonate (DEC) (4:2:4 %vol) solution in order to prepare polymer electrolyte membranes. The MPEGs PVDF/PVP/Nanoclay was applied using central composite design (CCD) experimental design to obtain a quantitative relationship between selected membranes prepared parameters namely (PVDF, PVP as pore forming agent and nanoclay filler concentration) and Ionic conductivity MPEGs. The model was used to find the optimum ionic conductivity from polymer electrolyte membranes. The polymer electrolyte membranes show good ionic conductivity on the order of 6.3 - 8.7 x 10-3 S cm-1 at the ambient temperatures. The ionic conductivity tended to increase with PVP and nanoclay concentration and decrease with PVDF composition. The model predicted the maximum ionic conductivity of 8.47 x 10-3 S cm-1 when the PVDF, PVP and nanoclay concentration were set at 8.01 %, 8.04 % and 10.12%, respectively. The first section in your paper.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2016-06-30

A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

PubMed

Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

2016-01-13

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Solid state ionics: a Japan perspective

NASA Astrophysics Data System (ADS)

Yamamoto, Osamu

2017-12-01

The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term 'solid state ionics' was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1-xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm-1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm-1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology.

Magneto-transport Characterization of Thin Film In-plane and Cross-plane Conductivity

NASA Astrophysics Data System (ADS)

Tang, Yang; Grayson, Matthew

Thin films with highly anisotropic in-plane and cross-plane conductivities are widely used in devices, such as infrared emitters and detectors, and the proper magneto-transport characterization in both directions can reveal information about the doping density, impurities, carrier life times and band structure. This work introduces a novel method for deducing the complete anisotropic electrical conductivity tensor of such an anisotropic resistive layer atop a highly conducting bottom contact, which is a standard part of the device structure. Three strip-line contacts separated by a length scale comparable to the film thickness are applied atop the resistive thin film layer of interest, with the highly conducting back-plane as a back-contact. The potential distribution in the device is modeled, using both scaling and conformal transformation to minimize the calculated volume. As a proof of concept, triple strip-line devices for GaAs and GaAs/AlGaAs superlattice thin films are fabricated. To achieve narrow strip-line contacts with sub-micron scale widths, non-annealed Ni/Au contacts form ohmic contacts to a patterned n+-GaAs cap layer atop the anisotropic thin films. Preliminary experimental data will be presented as a validation of this method. Acknowledgment: Funded by AFOSR FA9550-15-1-0377 and AFOSR FA9550-15-1-0247.

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation.

PubMed

Liang, Ting; van Kuringen, Huub P C; Mulder, Dirk J; Tan, Shuai; Wu, Yong; Borneman, Zandrie; Nijmeijer, Kitty; Schenning, Albertus P H J

2017-10-11

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.

Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

PubMed

Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

2017-11-30

Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

Induction log responses to layered, dipping, and anisotropic formations: Induction log shoulder-bed corrections to anisotropic formations and the effect of shale anisotropy in thinly laminated sand/shale sequences

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

Hagiwara, Teruhiko

1996-12-31

Induction log responses to layered, dipping, and anisotropic formations are examined analytically. The analytical model is especially helpful in understanding induction log responses to thinly laminated binary formations, such as sand/shale sequences, that exhibit macroscopically anisotropic: resistivity. Two applications of the analytical model are discussed. In one application we examine special induction log shoulder-bed corrections for use when thin anisotropic beds are encountered. It is known that thinly laminated sand/shale sequences act as macroscopically anisotropic: formations. Hydrocarbon-bearing formations also act as macroscopically anisotropic formations when they consist of alternating layers of different grain-size distributions. When such formations are thick, inductionmore » logs accurately read the macroscopic conductivity, from which the hydrocarbon saturation in the formations can be computed. When the laminated formations are not thick, proper shoulder-bed corrections (or thin-bed corrections) should be applied to obtain the true macroscopic formation conductivity and to estimate the hydrocarbon saturation more accurately. The analytical model is used to calculate the thin-bed effect and to evaluate the shoulder-bed corrections. We will show that the formation resistivity and hence the hydrocarbon saturation are greatly overestimated when the anisotropy effect is not accounted for and conventional shoulder-bed corrections are applied to the log responses from such laminated formations.« less

Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

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

Praveen, D.; Damle, Ramakrishna

2016-05-23

Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO{sub 4}){sub 2}, NH{sub 4}I etc., have already been tried in the past with some success. Also various nanoparticles like Al{sub 2}O{sub 3}, TiO{sub 2} etc., have been tried in themore » past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.« less

Finite-volume scheme for anisotropic diffusion

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

Es, Bram van, E-mail: bramiozo@gmail.com; FOM Institute DIFFER, Dutch Institute for Fundamental Energy Research, The Netherlands"1; Koren, Barry

In this paper, we apply a special finite-volume scheme, limited to smooth temperature distributions and Cartesian grids, to test the importance of connectivity of the finite volumes. The area of application is nuclear fusion plasma with field line aligned temperature gradients and extreme anisotropy. We apply the scheme to the anisotropic heat-conduction equation, and compare its results with those of existing finite-volume schemes for anisotropic diffusion. Also, we introduce a general model adaptation of the steady diffusion equation for extremely anisotropic diffusion problems with closed field lines.

Conductivity-Relaxation Relations in Nanocomposite Polymer Electrolytes Containing Ionic Liquid.

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

In this study, we have used nanocomposite polymer electrolytes, consisting of poly(ethylene oxide) (PEO), δ-Al 2 O 3 nanoparticles, and lithium bis(trifluoromethanesolfonyl)imide (LiTFSI) salt (with 4 wt % δ-Al 2 O 3 and PEO:Li ratios of 16:1 and 8:1), and added different amounts of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesolfonyl)imide (BMITFSI). The aim was to elucidate whether the ionic liquid is able to dissociate the Li-ions from the ether oxygens and thereby decouple the ionic conductivity from the segmental polymer dynamics. The results from DSC and dielectric spectroscopy show that the ionic liquid speeds up both the segmental polymer dynamics and the motion of the Li + ions. However, a close comparison between the structural (α) relaxation process, given by the segmental polymer dynamics, and the ionic conductivity shows that the motion of the Li + ions decouples from the segmental polymer dynamics at higher concentrations of the ionic liquid (≥20 wt %) and instead becomes more related to the viscosity of the ionic liquid. This decoupling increases with decreasing temperature. In addition to the structural α-relaxation, two more local relaxation processes, denoted β and γ, are observed. The β-relaxation becomes slightly faster at the highest concentration of the ionic liquid (at least for the lower salt concentration), whereas the γ-relaxation is unaffected by the ionic liquid, over the whole concentration range 0-40 wt %.

Lithium conductivity in an Li-bearing double-ring silicate mineral, sogdianite

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

Park, S.-H.; Hoelzel, M.; Forschungsneutronenquelle Heinz Maier-Leibnitz

The crystal structure of an Li-bearing double-ring silicate mineral, sogdianite ((Zr{sub 1.18}Fe{sup 3+} {sub 0.55}Ti{sub 0.24}Al{sub 0.03})(Y {sub 1.64},Na{sub 0.36})K{sub 0.85}[Li{sub 3}Si{sub 12}O{sub 30}], P6/mcc, a{approx}10.06 A, c{approx}14.30 A, Z=2), was investigated by neutron powder diffraction from 300 up to 1273 K. Rietveld refinements of displacement parameters revealed high anisotropic Li motions perpendicular to the crystallographic c-axis, indicating an exchange process between tetrahedral T2 and octahedral A sites. AC impedance spectra of a sogdianite single crystal (0.04x0.09x0.25 cm{sup 3}) show that the material is an ionic conductor with conductivity values of {sigma}=4.1x10{sup -5} S cm{sup -1} at 923 K andmore » 1.2x10{sup -3} S cm{sup -1} at 1219 K perpendicular to the c-axis, involving two relaxation processes with activation energies of 1.26(3) and 1.08(3) eV, respectively. - Graphical abstract: Structure of sogdianite with atomic displacement parameter (ADP) ellipsoids at 1273 K.« less

Hierarchical architecture of ReS2/rGO composites with enhanced electrochemical properties for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Qi, Fei; Chen, Yuanfu; Zheng, Binjie; He, Jiarui; Li, Qian; Wang, Xinqiang; Lin, Jie; Zhou, Jinhao; Yu, Bo; Li, Pingjian; Zhang, Wanli

2017-08-01

Rhenium disulfide (ReS2), a two-dimensional (2D) semiconductor, has attracted more and more attention due to its unique anisotropic electronic, optical, mechanical properties. However, the facile synthesis and electrochemical property of ReS2 and its composite are still necessary to be researched. In this study, for the first time, the ReS2/reduced graphene oxide (rGO) composites have been synthesized through a facile and one-pot hydrothermal method. The ReS2/rGO composites exhibit a hierarchical, interconnected, and porous architecture constructed by nanosheets. As anode for lithium-ion batteries, the as-synthesized ReS2/rGO composites deliver a large initial capacity of 918 mAh g-1 at 0.2 C. In addition, the ReS2/rGO composites exhibit much better electrochemical cycling stability and rate capability than that of bare ReS2. The significant enhancement in electrochemical property can be attributed to its unique architecture constructed by nanosheets and porous structure, which can allow for easy electrolyte infiltration, efficient electron transfer, and ionic diffusion. Furthermore, the graphene with high electronic conductivity can provide good conductive passageways. The facile synthesis approach can be extended to prepare other 2D transition metal dichalcogenides semiconductors for energy storage and catalytic application.

Line patterning of anisotropic spin chains by polarized laser for application in micro-thermal management

NASA Astrophysics Data System (ADS)

Terakado, Nobuaki; Takahashi, Ryosuke; Takahashi, Yoshihiro; Fujiwara, Takumi

2017-05-01

The control of heat flow has become increasingly important in energy saving and harvesting. Among various thermal management materials, spinon thermal conductivity materials are promising for heat flow control at microscales because they exhibit high, anisotropic thermal conductivity resulting from spin chains. However, there has been only little development of the materials for controlling heat flow. Here, we present the line patterning of the spin chain structure on a SrCuO2 nanocrystalline film by laser scanning. When the polarization direction of laser light was orthogonal to the scanning direction, we found that the spin-chain structure anisotropically grew on the patterned line.

Quantum transport in Dirac materials: Signatures of tilted and anisotropic Dirac and Weyl cones

NASA Astrophysics Data System (ADS)

Trescher, Maximilian; Sbierski, Björn; Brouwer, Piet W.; Bergholtz, Emil J.

2015-03-01

We calculate conductance and noise for quantum transport at the nodal point for arbitrarily tilted and anisotropic Dirac or Weyl cones. Tilted and anisotropic dispersions are generic in the absence of certain discrete symmetries, such as particle-hole and lattice point group symmetries. Whereas anisotropy affects the conductance g , but leaves the Fano factor F (the ratio of shot noise power and current) unchanged, a tilt affects both g and F . Since F is a universal number in many other situations, this finding is remarkable. We apply our general considerations to specific lattice models of strained graphene and a pyrochlore Weyl semimetal.

Studies on structural, thermal and AC conductivity scaling of PEO-LiPF6 polymer electrolyte with added ionic liquid [BMIMPF6

NASA Astrophysics Data System (ADS)

Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.

2015-07-01

Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.

Proton-conducting ionic liquid-based Proton Exchange Membrane Fuel Cell membranes: The key role of ionomer-ionic liquid interaction

NASA Astrophysics Data System (ADS)

Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves

The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.

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

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

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

Anisotropic proton-conducting membranes prepared from swift heavy ion-beam irradiated ETFE films

NASA Astrophysics Data System (ADS)

Kimura, Yosuke; Chen, Jinhua; Asano, Masaharu; Maekawa, Yasunari; Katakai, Ryoichi; Yoshida, Masaru

2007-10-01

Poly(ethylene-co-tetrafluoroethylene) (ETFE) films were irradiated by swift heavy ion-beams of 129Xe 23+ with fluences of 0, 3 × 10 6, 3 × 10 7, 3 × 10 8 and 3 × 10 9 ions/cm 2, followed by γ-ray pre-irradiation for radiation grafting of styrene onto the ETFE films and sulfonation of the grafted ETFE films to prepare highly anisotropic proton-conducting membranes. The fluence of Xe ions and the addition of water in the grafting solvent were examined to determine their effect on the proton conductivity of the resultant membranes. It was found that the polymer electrolyte membrane prepared by grafting the styrene monomer in a mixture of 67% isopropanol and 33% water to the ETFE film with an ion-beam irradiation fluence of 3.0 × 10 6 ions/cm 2 was a highly anisotropic proton-conducting material, as the proton conductivity was three or more times higher in the thickness direction than in the surface direction of the membrane.

Dielectric study on mixtures of ionic liquids.

PubMed

Thoms, E; Sippel, P; Reuter, D; Weiß, M; Loidl, A; Krohns, S

2017-08-07

Ionic liquids are promising candidates for electrolytes in energy-storage systems. We demonstrate that mixing two ionic liquids allows to precisely tune their physical properties, like the dc conductivity. Moreover, these mixtures enable the gradual modification of the fragility parameter, which is believed to be a measure of the complexity of the energy landscape in supercooled liquids. The physical origin of this index is still under debate; therefore, mixing ionic liquids can provide further insights. From the chemical point of view, tuning ionic liquids via mixing is an easy and thus an economic way. For this study, we performed detailed investigations by broadband dielectric spectroscopy and differential scanning calorimetry on two mixing series of ionic liquids. One series combines an imidazole based with a pyridine based ionic liquid and the other two different anions in an imidazole based ionic liquid. The analysis of the glass-transition temperatures and the thorough evaluations of the measured dielectric permittivity and conductivity spectra reveal that the dynamics in mixtures of ionic liquids are well defined by the fractions of their parent compounds.

Conductivities of the ionic complexes of two cyclic polyethers

NASA Technical Reports Server (NTRS)

Fielder, W. L.; Odonnell, P. M.

1975-01-01

The conductivities of the solid potassium thiocyanate complex of both dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 were measured at 300K (27 C). Saturated aqueous potassium thiocyanate and graphite were used as ion-transporting and ion-blocking electrodes, respectively. The ionic conductivity predominated for both samples, but it was many orders of magnitude smaller than the value previously reported. The ionic conductivity of the dicyclohexyl complex (the better conductor) was 0.000003 ohm/cm. Crown complexes, in general, do not appear promising as potassium ion solid electrolytes contrary to claims in the patent literature.

An electroactive conducting polymer actuator based on NBR/RTIL solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2007-04-01

This paper reports the fabrication of a dry-type conducting polymer actuator using nitrile rubber (NBR) as the base material in a solid polymer electrolyte. The conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique. Room-temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X (where X = BF4-, PF6-, (CF3SO2)2N-), were absorbed into the composite film. The compatibility between the ionic liquids and the NBR polymer was confirmed by DMA. The effect of the anion size of the ionic liquids on the displacement of the actuator was examined. The displacement increased with increasing anion size of the ionic liquids. The cyclic voltammetry responses and the redox switching dynamics of the actuators were examined in different ionic liquids.

Development and Characterization of Poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer Based Polymer Electrolytes

PubMed Central

Sa'adun, Nurul Nadiah; Subramaniam, Ramesh; Kasi, Ramesh

2014-01-01

Gel polymer electrolytes (GPEs) are developed using poly(1-vinylpyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] as the host polymer, lithium bis(trifluoromethane) sulfonimide [LiTFSI] as the lithium salt and ionic liquid, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMImTFSI] by using solution casting technique. The effect of ionic liquid on ionic conductivity is studied and the optimum ionic conductivity at room temperature is found to be 2.14 × 10−6 S cm−1 for sample containing 25 wt% of EMImTFSI. The temperature dependence of ionic conductivity from 303 K to 353 K exhibits Arrhenius plot behaviour. The thermal stability of the polymer electrolyte system is studied by using thermogravimetric analysis (TGA) while the structural and morphological properties of the polymer electrolyte is studied by using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis (XRD), respectively. PMID:25431781

Molecular dynamics simulation of the ionic liquid N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2007-10-11

Thermodynamics, structure, and dynamics of an ionic liquid based on a quaternary ammonium salt with ether side chain, namely, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, MOENM2E TFSI, are investigated by molecular dynamics (MD) simulations. Average density and configurational energy of simulated MOENM2E TFSI are interpreted with models that take into account empirical ionic volumes. A throughout comparison of the equilibrium structure of MOENM2E TFSI with previous results for the more common ionic liquids based on imidazolium cations is provided. Several time correlation functions are used to reveal the microscopic dynamics of MOENM2E TFSI. Structural relaxation is discussed by the calculation of simultaneous space-time correlation functions. Temperature effects on transport coefficients (diffusion, conductivity, and viscosity) are investigated. The ratio between the actual conductivity and the estimate from ionic diffusion by the Nernst-Einstein equation indicates that correlated motion of neighboring ions in MOENM2E TFSI is similar to imidazolium ionic liquids. In line with experiment, Walden plot of conductivity and viscosity indicates that simulated MOENM2E TFSI should be classified as a poor ionic liquid.

Role of succinonitrile in improving ionic conductivity of sodium-ion conductive polymer electrolyte

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Mohapatra, Saumya R.

2018-05-01

Sodium ion conducting solid polymer electrolytes were prepared using poly (ethylene oxide) (PEO) as polymer matrix, sodium perchlorate (NaClO4) as salt and succinonitrile (SN) as a plasticizer by solution casting technique. By blending a plastic crystal such as succinonitrile (SN) with PEO-NaClO4 electrolyte system, we aimed at improving the ionic conductivity by weakening the ether oxygen-Na+ interactions. The XRD and FTIR studies revealed structural and micro-structural changes in the blended electrolytes which aids in improving ionic conductivity. Also, DSC measurements showed improved segmental motion in the blended polymer electrolytes due to plasticizing effect of SN. The maximum ionic conductivity observed at room temperature is 1.13×10-5 S cm-1 merely for 7 wt. % of SN, which is one order higher than pure polymer-salt complex. The thermo-gravimetric analysis (TGA) suggests that blending of SN with polymer electrolyte had no detrimental effect on its thermal stability.

Properties of the Nafion membrane impregnated with hydroxyl ammonium based ionic liquids

NASA Astrophysics Data System (ADS)

Garaev, Valeriy; Kleperis, Janis; Pavlovica, Sanita; Vaivars, Guntars

2012-08-01

In this work, the Nafion 112 membrane impregnated with nine various hydroxyl ammonium based ionic liquids have been investigated. The used ionic liquids were combined from hydroxyl ammonium cations (2-hydroxyethylammonium/HEA, bis(2- hydroxyethyl)ammonium/BHEA, tris(2-hydroxyethyl)ammonium/THEA) and carboxylate anions (formate, acetate, lactate). The membranes are characterized by conductivity and thermal stability measurements. It was found, that almost all composites have 10 times higher ion conductivity than a pure Nafion 112 at 90 °C in ambient environment due to the higher thermal stability. The thermal stability of Nafion membrane was increased by all studied nine ionic liquids. In this work, only biodegradable ionic liquids were used for composite preparation.

BUOYANCY INSTABILITIES IN A WEAKLY COLLISIONAL INTRACLUSTER MEDIUM

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

Kunz, Matthew W.; Stone, James M.; Bogdanovic, Tamara

2012-08-01

The intracluster medium (ICM) of galaxy clusters is a weakly collisional plasma in which the transport of heat and momentum occurs primarily along magnetic-field lines. Anisotropic heat conduction allows convective instabilities to be driven by temperature gradients of either sign: the magnetothermal instability (MTI) in the outskirts of clusters and the heat-flux buoyancy-driven instability (HBI) in their cooling cores. We employ the Athena magnetohydrodynamic code to investigate the nonlinear evolution of these instabilities, self-consistently including the effects of anisotropic viscosity (i.e., Braginskii pressure anisotropy), anisotropic conduction, and radiative cooling. We find that, in all but the innermost regions of cool-coremore » clusters, anisotropic viscosity significantly impairs the ability of the HBI to reorient magnetic-field lines orthogonal to the temperature gradient. Thus, while radio-mode feedback appears necessary in the central few Multiplication-Sign 10 kpc, heat conduction may be capable of offsetting radiative losses throughout most of a cool core over a significant fraction of the Hubble time. Magnetically aligned cold filaments are then able to form by local thermal instability. Viscous dissipation during cold filament formation produces accompanying hot filaments, which can be searched for in deep Chandra observations of cool-core clusters. In the case of MTI, anisotropic viscosity leads to a nonlinear state with a folded magnetic field structure in which field-line curvature and field strength are anti-correlated. These results demonstrate that, if the HBI and MTI are relevant for shaping the properties of the ICM, one must self-consistently include anisotropic viscosity in order to obtain even qualitatively correct results.« less

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects.

PubMed

Pastor, María Jesús; Cuerva, Cristián; Campo, José A; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-05-12

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO R(n)pyH ]⁺ and BF₄ - , ReO₄ - , NO₃ - , CF₃SO₃ - , CuCl₄ 2- counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO R(12)pyH ][ReO₄] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl₄ 2- salts exhibit the best LC properties followed by the ReO₄ - ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO₄ - , and CuCl₄ 2- families, and for the solid phase in one of the non-mesomorphic Cl - salts. The highest ionic conductivity was found for the smectic mesophase of the ReO₄ - containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.

Improper magnetic ferroelectricity of nearly pure electronic nature in helicoidal spiral CaMn7O12

NASA Astrophysics Data System (ADS)

Lim, Jin Soo; Saldana-Greco, Diomedes; Rappe, Andrew M.

2018-01-01

Helicoidal magnetic order breaks inversion symmetry in quadruple perovskite CaMn7O12 , generating one of the largest spin-induced ferroelectric polarizations measured to date. Here, the microscopic origin of the polarization, including exchange interactions, coupling to the spin helicity, and charge density redistribution, is explored via first-principles calculations. The B -site Mn4 + (Mn3) spin adopts a noncentrosymmetric configuration, stabilized not only by spin-orbit coupling (SOC), but also by the fully anisotropic Hubbard J parameter in the absence of SOC, to break inversion symmetry and generate polarization. Berry phase computed polarization (Pelec=2169 μ C /m2 ) exhibits nearly pure electronic behavior, with negligible Mn displacements (≈0.7 m Å ). Orbital-resolved density of states shows that p -d orbital mixing is microscopically driven by nonrelativistic exchange striction within the commensurate ionic structure. Persistent electronic polarization induced by helical spin order in the nearly inversion-symmetric ionic crystal lattice suggests opportunities for ultrafast magnetoelectric response.

Hydrodynamic interpretation on the rotational diffusion of peroxylamine disulfonate solute dissolved in room temperature ionic liquids as studied by electron paramagnetic resonance spectroscopy.

PubMed

Miyake, Yusuke; Akai, Nobuyuki; Kawai, Akio; Shibuya, Kazuhiko

2011-06-23

Rotational motion of a nitroxide radical, peroxylamine disulfonate (PADS), dissolved in room temperature ionic liquids (RTILs) was studied by analyzing electron paramagnetic resonance spectra of PADS in various RTILs. We determined physical properties of PADS such as the hyperfine coupling constant (A), the temperature dependence of anisotropic rotational correlation times (τ(∥) and τ(⊥)), and rotational anisotropy (N). We observed that the A values remain unchanged for various RTILs, which indicates negligible interaction between the N-O PADS group and the cation of RTIL. Large N values suggest strong interaction of the negative sulfonyl parts of PADS with the cations of RTILs. Most of the τ(∥), τ(⊥), and (τ(∥)τ(⊥))(1/2) values are within the range calculated on the basis of a hydrodynamic theory with stick and slip boundary conditions. It was deduced that this theory could not adequately explain the measured results in some RTILs with smaller BF(4) and PF(6) anions.

A novel conductance glucose biosensor in ultra-low ionic strength solution triggered by the oxidation of Ag nanoparticles.

PubMed

Song, Yonghai; Chen, Jingyi; Liu, Hongyu; Li, Ping; Li, Hongbo; Wang, Li

2015-09-03

A simple, sensitive and effective method to detect glucose in ultra-low ionic strength solution containing citrate-capped silver nanoparticles (CCAgNPs) was developed by monitoring the change of solution conductance. Glucose was catalyzed into gluconic acid firstly by glucose oxidase in an O2-saturated solution accompanied by the reduction of O2 into hydrogen peroxide (H2O2). Then, CCAgNPs was oxidized by H2O2 into Ag(+) and the capping regent of citrate was released at the same time. All these resulted Ag(+), gluconic acid and the released citrate would contribute to the increase of solution ionic strength together, leading to a detectable increase of solution conductance. And a novel conductance glucose biosensor was developed with a routine linear range of 0.06-4.0 mM and a suitable detection limit of 18.0 μM. The novel glucose biosensor was further applied in energy drink sample and proven to be suitable for practical system with low ionic strength. The proposed conductance biosensor achieved a significant breakthrough of glucose detection in ultra-low ionic strength media. Copyright © 2015 Elsevier B.V. All rights reserved.

High H⁻ ionic conductivity in barium hydride.

PubMed

Verbraeken, Maarten C; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T S

2015-01-01

With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

Mesoscopic Framework Enables Facile Ionic Transport in Solid Electrolytes for Li Batteries

DOE PAGES

Ma, Cheng; Cheng, Yongqiang; Chen, Kai; ...

2016-03-29

In Li-ion-conducting solid electrolytes can simultaneously overcome two grand challenges for Li-ion batteries: the severe safety concerns that limit the large-scale application and the poor electrolyte stability that forbids the use of high-voltage cathodes. Nevertheless, the ionic conductivity of solid electrolytes is typically low, compromising the battery performances. Precisely determining the ionic transport mechanism(s) is a prerequisite for the rational design of highly conductive solid electrolytes. For decades, the research on this subject has primarily focused on the atomic and microscopic scales, where the main features of interest are unit cells and microstructures, respectively. We show that the largely overlookedmore » mesoscopic scale lying between these extremes could be the key to fast ionic conduction. In a prototype system, (Li 0.33La 0.56)TiO 3, a mesoscopic framework is revealed for the first time by state-of-the-art scanning transmission electron microscopy. Corroborated by theoretical calculations and impedance measurements, it is demonstrated that such a unique configuration maximizes the number of percolation directions and thus most effectively improves the ionic conductivity. Finally, this discovery reconciles the long-standing structure–property inconsistency in (Li 0.33La 0.56)TiO 3 and also identifies mesoscopic ordering as a promising general strategy for optimizing Li+ conduction.« less

Structural and Dielectric Properties of Ionic Liquid Doped Metal Organic Framework based Polymer Electrolyte Nanocomposites

NASA Astrophysics Data System (ADS)

Dutta, Rituraj; Kumar, Ashok

2016-10-01

Metal Organic Frameworks (MOFs) are mesoporous materials that can be treated as potential hosts for trapping guest molecules in their pores. Ion conduction and phase behavior dynamics of Ionic Liquids (ILs) can be controlled by tunable interactions of MOFs with the ILs. MOFs incorporated with ionic liquid can be dispersed in the polymers to synthesize polymer electrolyte nanocomposites with high ionic conductivity, electrochemical and thermal stability for applications in energy storage and conversion devices such as rechargeable Li-ion batteries. In the present work we have synthesized Cu-based MOF [Cu3(l,3,5-benzene tricarboxylate)2(H2O)] incorporated with the ionic liquid 1-Butyl-3-methylimidazolium bromide at different weight ratios of MOF and IL. The synthesized MOF-IL composites are dispersed in Poly (ethylene oxide) (PEO). Frequency dependent behavior of permittivity and dielectric loss of the nanocomposites depict the non-Debye dielectric relaxation mechanism. The room temperature Nyquist plots reveal decreasing bulk resistance upto 189 Ω with optimum ionic conductivity of 1.3×10-3S cm-1at maximum doping concentration of IL in the nanocomposite system.

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

A Numerical Study of Scalable Cardiac Electro-Mechanical Solvers on HPC Architectures

PubMed Central

Colli Franzone, Piero; Pavarino, Luca F.; Scacchi, Simone

2018-01-01

We introduce and study some scalable domain decomposition preconditioners for cardiac electro-mechanical 3D simulations on parallel HPC (High Performance Computing) architectures. The electro-mechanical model of the cardiac tissue is composed of four coupled sub-models: (1) the static finite elasticity equations for the transversely isotropic deformation of the cardiac tissue; (2) the active tension model describing the dynamics of the intracellular calcium, cross-bridge binding and myofilament tension; (3) the anisotropic Bidomain model describing the evolution of the intra- and extra-cellular potentials in the deforming cardiac tissue; and (4) the ionic membrane model describing the dynamics of ionic currents, gating variables, ionic concentrations and stretch-activated channels. This strongly coupled electro-mechanical model is discretized in time with a splitting semi-implicit technique and in space with isoparametric finite elements. The resulting scalable parallel solver is based on Multilevel Additive Schwarz preconditioners for the solution of the Bidomain system and on BDDC preconditioned Newton-Krylov solvers for the non-linear finite elasticity system. The results of several 3D parallel simulations show the scalability of both linear and non-linear solvers and their application to the study of both physiological excitation-contraction cardiac dynamics and re-entrant waves in the presence of different mechano-electrical feedbacks. PMID:29674971

Ionic conductivity and dielectric permittivity of polymer electrolyte plasticized with polyethylene glycol

NASA Astrophysics Data System (ADS)

Das, S.; Ghosh, A.

2016-05-01

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with polyethylene glycol (PEG). The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. The maximum dielectric constant is observed for 30 wt. % of PEG content. To get further insights into the ion dynamics, the complex dielectric permittivity has been studied with Havriliak-Negami function. The variation of relaxation time with inverse temperature obtained from HN formalism follows VTF nature.

Effect of nanochitosan and succinonitrile on the AC ionic conductivity of plasticized nanocomposite solid polymer electrolytes (PNCSPE)

NASA Astrophysics Data System (ADS)

Karuppasamy, K.; Vani, C. Vijil; Nichelson, A.; Balakumar, S.; Shajan, X. Sahaya

2013-06-01

In the present study, the filler chitosan was converted into nanochitosan by ionotropic gelation method. Plasticized nanocomposite solid polymer electrolytes (PNCSPE) composed of poly ethylene oxide as host polymer, LiBOB (lithium bis(oxalatoborate)) as salt, SN as plasticizer and nanochitosan as filler were prepared by membrane hot-press technique. Succinonitrile and nanochitosan incorporation in PEO-LiBOB matrix enhanced the room temperature ionic conductivity. The highest ionic conductivities were found to be in the order of 10-3.2 S/cm.

Lithium ion conducting ionic electrolytes

DOEpatents

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

1996-01-16

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

Lithium ion conducting ionic electrolytes

DOEpatents

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

1996-01-01

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

Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

PubMed

Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

2017-07-01

Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (T g ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm -1 ) and T g (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A small-plane heat source method for measuring the thermal conductivities of anisotropic materials

NASA Astrophysics Data System (ADS)

Cheng, Liang; Yue, Kai; Wang, Jun; Zhang, Xinxin

2017-07-01

A new small-plane heat source method was proposed in this study to simultaneously measure the in-plane and cross-plane thermal conductivities of anisotropic insulating materials. In this method the size of the heat source element is smaller than the sample size and the boundary condition is thermal insulation due to no heat flux at the edge of the sample during the experiment. A three-dimensional model in a rectangular coordinate system was established to exactly describe the heat transfer process of the measurement system. Using the Laplace transform, variable separation, and Laplace inverse transform methods, the analytical solution of the temperature rise of the sample was derived. The temperature rises calculated by the analytical solution agree well with the results of numerical calculation. The result of the sensitivity analysis shows that the sensitivity coefficients of the estimated thermal conductivities are high and uncorrelated to each other. At room temperature and in a high-temperature environment, experimental measurements of anisotropic silica aerogel were carried out using the traditional one-dimensional plane heat source method and the proposed method, respectively. The results demonstrate that the measurement method developed in this study is effective and feasible for simultaneously obtaining the in-plane and cross-plane thermal conductivities of the anisotropic materials.

Novel polymeric LIT and divalent cation fast ion conducting materials

NASA Astrophysics Data System (ADS)

Angell, C. A.

Solid state energy devices require a component which conducts electricity by ionic migration. The conductivity of this element of the system must be very high. Four types of materials show the promise to provide the necessary conductivity characteristics, while offering other desirable features such as the ability to distort in shape under mechanical stresses: (1) crystalline; (2) plastic crystal; (3) inorganic glassy; and (4) polymer salt solutions. This document reports on the following materials: lead halide-containing fast ion conducting glasses (LiF-PbF2-Al(PO3)3), mixed ionic electronic conduction (Na2O-V2O5-TeO2), alpha relaxation in ionic glasses, glass transition in P2O2, and conductivity transition between all-halide and all-oxide glasses.

Fabrication methods and anisotropic properties of graphite matrix compacts for use in HTGR

NASA Astrophysics Data System (ADS)

Yeo, Sunghwan; Yun, Jihae; Kim, Sungok; Cho, Moon Sung; Lee, Young-Woo

2018-02-01

This study investigated the anisotropic microstructural, mechanical, and thermal properties of fabricated graphite matrix prismatic compacts for High Temperature Gas Cooled Reactor (HTGR) fuel. When the observed alignment of graphite grains and the coke derived from phenolic resin is in the transverse direction, the result is severely anisotropic thermal properties. Compacts with such orientation in the transverse direction exhibited increases of thermal expansion and conductivity up to 5.8 times and 4.82 times, respectively, more than those in the axial direction. The formation of pores due to the pyrolysis of phenolic resin was observed predominantly on upper region of the fabricated compacts. This anisotropic pore formation created anisotropic Vickers hardness on the planes with different directions.

NMR Studies of Mass Transport in New Conducting Media for Fuel Cells

DTIC Science & Technology

2009-01-01

PEM films, for example those containing phosphoric acid and ionic liquids . Dynamical processes are probed at the short range by spin-lattice...structural environments of muticomponent PEM films, for example those containing phosphoric acid and ionic liquids . Dynamical processes are probed at the...correlation between water diffusivity and proton conductivity in the nanocomposites Transport properties of several ionic liquids (IL’s) and membranes

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

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

Fan, Fei; Wang, Yangyang; Hong, Tao

2015-07-17

Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore » from the ideal line increases upon approaching the glass transition temperature (T g). Moreover, the conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. Finally, we relate this observation to a decrease in polymer packing efficiency with an increase in fragility.« less

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

DOE PAGES

Seol, Daehee; Seo, Hosung; Jesse, Stephen; ...

2015-08-19

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. Finally, these results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

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

Seol, Daehee; Seo, Hosung; Jesse, Stephen

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. Finally, these results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

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

Seol, Daehee; Seo, Hosung; Kim, Yunseok, E-mail: yunseokkim@skku.edu

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. These results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Gel polymer electrolytes for batteries

DOEpatents

Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

2014-11-18

Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

Effect of alcaline cations in zeolites on their dielectric properties.

PubMed

Legras, Benoît; Polaert, Isabelle; Estel, Lionel; Thomas, Michel

2012-01-01

The effect on dielectric properties of alkaline cations Li+, Na+ and K+ incorporated in a zeolite Faujasite structure X or Y, has been investigated. Two major phenomena have been proved to occur: ionic conductivity and rotational polarization of the water molecules adsorbed. The polarizability of the cation which is directly linked to its radius, affects ionic conductivity as well as rotational polarization. Li cations are more strongly Linked to the framework than K+ and Na+ and induce a lower ionic conductivity. K+ is weakly fixed and induces a ionic conductivity even at low solvation level. At low water content, the cation nature and number mainly control the free rotation of the water molecules and affect the relaxation frequency. Close to saturation, the water molecules are mainly linked together by H bonds: the cation nature and number do not really affect the global dielectric properties anymore.

Polymer Ni-MH battery based on PEO-PVA-KOH polymer electrolyte

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen

An alkaline polymer electrolyte film has been prepared by a solvent-casting method. Poly(vinyl alcohol), PVA is added to improve the ionic conductivity of the electrolyte. The ionic conductivity increases from 10 -7 to 10 -2 S cm -1 at room temperature when the weight percent ratio of poly(ethylene oxide), PEO to PVA is increased from 10:0 to 5:5. The activation energy of the ionic conductivity for the PEO-PVA-KOH polymer electrolyte is 3-8 kJ mol -1. The properties of the electrolyte film are characterized by a wide variety of techniques and it is found that the film exhibits good mechanical stability and high ionic conductivity at room temperature. The application of such electrolyte films to nickel-metal-hydride (Ni-MH) batteries is examined and the electrochemical characteristics of a polymer Ni-MH battery are obtained.

Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity?

PubMed

Düvel, Andre; Heitjans, Paul; Fedorov, Pavel; Scholz, Gudrun; Cibin, Giannantonio; Chadwick, Alan V; Pickup, David M; Ramos, Silvia; Sayle, Lewis W L; Sayle, Emma K L; Sayle, Thi X T; Sayle, Dean C

2017-04-26

Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors, and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF 2 , by ball milling it with BaF 2 , to create nanostructured Ba 1-x Ca x F 2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including "simulating synthesis", we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include structural disorder, excess volume, pseudovacancy arrays, and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba 1-x Ca x F 2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [ Nature 2015 , 521 , 303 ] remarks that classical crystallography is inadequate to describe systems with correlated disorder, but that correlated disorder has clear crystallographic signatures. Here, we identify two possible crystallographic signatures of geometric frustration: excess volume and correlated "snake-like" ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013 , 138 , 12A538 ]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, and branching of the "snake" arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous, or liquid states and processes such as ionic conductivity, melting, and crystallization.

Understanding the impact of nanoscale aggregation on charge transport and structural dynamics in room temperature ionic liquids

NASA Astrophysics Data System (ADS)

Griffin, Philip; Holt, Adam; Wang, Yangyang; Sokolov, Alexei

2015-03-01

Amphiphilic room temperature ionic liquids (ILs) segregate on the nanoscale, forming intricate networks of charge-rich ionic domains intercalated with charge-poor aliphatic domains. While this structural phenomenon has been well established through x-ray diffraction studies and atomistic MD simulations, the precise effects of nanophase segregation on ion transport and structural dynamics in ILs remains poorly understood. Using a combination of broadband dielectric spectroscopy, light scattering spectroscopy, and rheology, we have characterized the ionic conductivity, structural dynamics, and shear viscosity of a homologous series of quaternary ammonium ionic liquids over a wide temperature range. Upon increasing the length and volume fraction of the alkyl side chains of these quaternary ammonium ILs, ionic conductivity decreases precipitously, although no corresponding slowing of the structural dynamics is observed. Instead, we identify the dynamical signature of supramolecular aggregates. Our results directly demonstrate the role that chemical structure and ionic aggregation plays in determining the charge transport properties of amphiphilic ILs.

Growth and anisotropic thermal properties of biaxial Ho:YAlO3 crystal

NASA Astrophysics Data System (ADS)

Dong, Qin; Zhao, Guangjun; Chen, Jianyu; Ding, Yuchong; Zhao, Chengchun

2010-07-01

Ho:YAlO3 (YAP) crystal with large size and good optical quality has been grown by the Czochralski method. Thermal properties of the as-grown Ho:YAP crystal have been investigated by measuring the temperature-dependent, anisotropic thermal expansion, specific heat, thermal diffusion, and thermal conductivity. The results show that Ho:YAP crystal possesses a large anisotropic thermal expansion and good thermal conductivity. The calculated average thermal expansion coefficients along a, b, and c axis are αa=9.18×10-6/K, αb=1.94×10-6/K, and αc=7.61×10-6/K from 293.15 to 770.15 K. The thermal conductivities along a, b, and c axis are up to 11.6, 9.9, and 12.3 W m-1 K-1 at 298.15 K. Compared with Ho: Y3Al5O12 (YAG), Ho:YAP crystal has a larger thermal conductivity along a axis from 298.15 to 568.15 K.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

Ionic liquids and their solid-state analogues as materials for energy generation and storage

NASA Astrophysics Data System (ADS)

Macfarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.; Kar, Mega; Passerini, Stefano; Pringle, Jennifer M.; Ohno, Hiroyuki; Watanabe, Masayoshi; Yan, Feng; Zheng, Wenjun; Zhang, Shiguo; Zhang, Jie

2016-02-01

Salts that are liquid at room temperature, now commonly called ionic liquids, have been known for more than 100 years; however, their unique properties have only come to light in the past two decades. In this Review, we examine recent work in which the properties of ionic liquids have enabled important advances to be made in sustainable energy generation and storage. We discuss the use of ionic liquids as media for synthesis of electromaterials, for example, in the preparation of doped carbons, conducting polymers and intercalation electrode materials. Focusing on their intrinsic ionic conductivity, we examine recent reports of ionic liquids used as electrolytes in emerging high-energy-density and low-cost batteries, including Li-ion, Li-O2, Li-S, Na-ion and Al-ion batteries. Similar developments in electrolyte applications in dye-sensitized solar cells, thermo-electrochemical cells, double-layer capacitors and CO2 reduction are also discussed.

Computer aided design of nano-structured materials with tailored ionic conductivities.

PubMed

Sayle, Dean C; Doig, James A; Parker, Stephen C; Watson, Graeme W; Sayle, Thi X T

2005-01-07

We show, using simulation techniques, that the high ionic conductivity in BaF2/CaF2 heterolayers is because the interfaces reduce the activation energy barriers to mobility and increase the number of charge carriers.

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

2007-01-01

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Direct current dielectrophoretic manipulation of the ionic liquid droplets in water.

PubMed

Zhao, Kai; Li, Dongqing

2018-07-13

The ionic liquids (ILs) as the environmentally benign solvents show great potentials in microemulsion carrier systems and have been widely used in the biochemical and pharmaceutical fields. In the work, the ionic liquid-in-water microemulsions were fabricated by using two kinds of hydrophobic ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6 ] and 1-Hexyl-3-methylimidazolium hexafluorophosphate [Hmim][PF 6 ] with Tween 20. The ionic liquid droplets in water experience the dielectrophoretic (DEP) forces induced by applying electrical field via a nano-orifice and a micron orifice on the opposite channel walls of a microchannel. The dielectrophoretic behaviors of the ionic liquid-in-water emulsion droplets were investigated under direct current (DC) electric field. The positive and negative DEP behaviors of the ionic liquid-in-water droplets varying with the electrical conductivity of the suspending medium were investigated and two kinds of the ionic liquid droplets of similar sizes were separated by their different DEP behaviors. In addition, the separation of the ionic liquid-in-water droplets by size was conducted. This paper, for the first time to our knowledge, presents the DC-DEP manipulation of the ionic liquid-in-water emulsion droplets by size and by type. This method provides a platform to manipulate the ionic liquid droplets individually. Copyright © 2018 Elsevier B.V. All rights reserved.

Anisotropic conducting films for electromagnetic radiation applications

DOEpatents

Cavallo, Francesca; Lagally, Max G.; Rojas-Delgado, Richard

2015-06-16

Electronic devices for the generation of electromagnetic radiation are provided. Also provided are methods for using the devices to generate electromagnetic radiation. The radiation sources include an anisotropic electrically conducting thin film that is characterized by a periodically varying charge carrier mobility in the plane of the film. The periodic variation in carrier mobility gives rise to a spatially varying electric field, which produces electromagnetic radiation as charged particles pass through the film.

Optimal design of high temperature metalized thin-film polymer capacitors: A combined numerical and experimental method

NASA Astrophysics Data System (ADS)

Wang, Zhuo; Li, Qi; Trinh, Wei; Lu, Qianli; Cho, Heejin; Wang, Qing; Chen, Lei

2017-07-01

The objective of this paper is to design and optimize the high temperature metalized thin-film polymer capacitor by a combined computational and experimental method. A finite-element based thermal model is developed to incorporate Joule heating and anisotropic heat conduction arising from anisotropic geometric structures of the capacitor. The anisotropic thermal conductivity and temperature dependent electrical conductivity required by the thermal model are measured from the experiments. The polymer represented by thermally crosslinking benzocyclobutene (BCB) in the presence of boron nitride nanosheets (BNNSs) is selected for high temperature capacitor design based on the results of highest internal temperature (HIT) and the time to achieve thermal equilibrium. The c-BCB/BNNS-based capacitor aiming at the operating temperature of 250 °C is geometrically optimized with respect to its shape and volume. "Safe line" plot is also presented to reveal the influence of the cooling strength on capacitor geometry design.

Electrical screening procedure for solid ionic conductors

NASA Technical Reports Server (NTRS)

Kautz, H. E.; Singer, J.; Fielder, W. L.; Fordyce, J. S.

1973-01-01

An electrical screening method has been developed for preliminary evaluation of polycrystalline specimens of candidates for use as solid ionic conductive electrolytes in batteries. The procedure measures dielectric loss and capacitance, from which are calculated an ac conductivity attributed provisionally to ions and an activation energy for that conductivity. Electronic conductivity is directly measured. The screening procedure applied to sodium beta-alumina yielded acceptable values for conductivity and activation energy.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

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

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

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

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

2015-08-13

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

Anisotropic thermal property of magnetically oriented carbon nanotube polymer composites

NASA Astrophysics Data System (ADS)

Li, Bin; Dong, Shuai; Wang, Caiping; Wang, Xiaojie; Fang, Jun

2016-04-01

This paper proposes a method for preparing multi-walled carbon nanotubea/polydimethylsiloxane (MWCNTs/PDMS) composites with enhanced thermal properties by using a high magnetic field (up to 10T). The MWCNT are oriented magnetically inside a silicone by in-situ polymerization method. The anisotropic structure would be expected to produce directional thermal conductivity. This study will provide a new approach to the development of anisotropic thermal-conductive polymer composites. Systematic studies with the preparation of silicone/graphene composites corresponding to their thermal and mechanical properties are carried out under various conditions: intensity of magnetic field, time, temperature, fillings. The effect of MWCNT/graphene content and preparation procedures on thermal conductivity of composites is investigated. Dynamic mechanical analysis (DMA) is used to reveal the mechanical properties of the composites in terms of the filling contents and magnetic field strength. The scanning electron microscope (SEM) is used to observe the micro-structure of the MWCNT composites. The alignment of MWCNTs in PDMS matrix is also studied by Raman spectroscopy. The thermal conductivity measurements show that the magnetically aligned CNT-composites feature high anisotropy in thermal conductivity.

Ionic micelles and aromatic additives: a closer look at the molecular packing parameter.

PubMed

Lutz-Bueno, Viviane; Isabettini, Stéphane; Walker, Franziska; Kuster, Simon; Liebi, Marianne; Fischer, Peter

2017-08-16

Wormlike micellar aggregates formed from the mixture of ionic surfactants with aromatic additives result in solutions with impressive viscoelastic properties. These properties are of high interest for numerous industrial applications and are often used as model systems for soft matter physics. However, robust and simple models for tailoring the viscoelastic response of the solution based on the molecular structure of the employed additive are required to fully exploit the potential of these systems. We address this shortcoming with a modified packing parameter based model, considering the additive-surfactant pair. The role of charge neutralization on anisotropic micellar growth was investigated with derivatives of sodium salicylate. The impact of the additives on the morphology of the micellar aggregates is explained from the molecular level to the macroscopic viscoelasticity. Changes in the micelle's volume, headgroup area and additive structure are explored to redefine the packing parameter. Uncharged additives penetrated deeper into the hydrophobic region of the micelle, whilst charged additives remained trapped in the polar region, as revealed by a combination of 1 H-NMR, SAXS and rheological measurements. A deeper penetration of the additives densified the hydrophobic core of the micelle and induced anisotropic growth by increasing the effective volume of the additive-surfactant pair. This phenomenon largely influenced the viscosity of the solutions. Partially penetrating additives reduced the electrostatic repulsions between surfactant headgroups and neighboring micelles. The resulting increased network density governed the elasticity of the solutions. Considering a packing parameter composed of the additive-surfactant pair proved to be a facile means of engineering the viscoelastic response of surfactant solutions. The self-assembly of the wormlike micellar aggregates could be tailored to desired morphologies resulting in a specific and predictable rheological response.

Ionic conduction and self-diffusion near infinitesimal concentration in lithium salt-organic solvent electrolytes

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sugimoto, Kyoko; Price, William S.; Hayamizu, Kikuko

2000-08-01

The Debye-Hückel-Onsager and Nernst-Einstein equations, which are based on two different conceptual approaches, constitute the most widely used equations for relating ionic conduction to ionic mobility. However, both of these classical (simple) equations are predictive of ionic conductivity only at very low salt concentrations. In the present work the ionic conductivity of four organic solvent-lithium salt-based electrolytes were measured. These experimental conductivity values were then contrasted with theoretical values calculated using the translational diffusion (also known as self-diffusion or intradiffusion) coefficients of all of the species present obtained using pulsed-gradient spin-echo (1H, 19F and 7Li) nuclear magnetic resonance self-diffusion measurements. The experimental results verified the applicability of both theoretical approaches at very low salt concentrations for these particular systems as well as helping to clarify the reasons for the divergence between theory and experiment. In particular, it was found that the correspondence between the Debye-Hückel-Onsager equation and experimental values could be improved by using the measured solvent self-diffusion values to correct for salt-induced changes in the solution viscosity. The concentration dependence of the self-diffusion coefficients is discussed in terms of the Jones-Dole equation.

Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte

NASA Astrophysics Data System (ADS)

Kang, Joonhee; Chung, Habin; Doh, Chilhoon; Kang, Byoungwoo; Han, Byungchan

2015-10-01

Understanding of the fundamental mechanisms causing significant enhancement of Li-ionic conductivity by Al3+ doping to a solid LiGe2(PO4)3 (LGP) electrolyte is pursued using first principles density functional theory (DFT) calculations combined with experimental measurements. Our results indicate that partial substitution Al3+ for Ge4+ in LiGe2(PO4)3 (LGP) with aliovalent (Li1+xAlxGe2-x(PO4)3, LAGP) improves the Li-ionic conductivity about four-orders of the magnitude. To unveil the atomic origin we calculate plausible diffusion paths of Li in LGP and LAGP materials using DFT calculations and a nudged elastic band method, and discover that LAGP had additional transport paths for Li with activation barriers as low as only 34% of the LGP. Notably, these new atomic channels manifest subtle electrostatic environments facilitating cooperative motions of at least two Li atoms. Ab-initio molecular dynamics predict Li-ionic conductivity for the LAGP system, which is amazingly agreed experimental measurement on in-house made samples. Consequently, we suggest that the excess amounts of Li caused by the aliovalent Al3+ doping to LGP lead to not only enhancing Li concentration but also opening new conducting paths with substantially decreases activation energies and thus high ionic conductivity of LAGP solid-state electrolyte.

Influence of temperature and frequency on ionic conductivity of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses

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

El Moudane, M., E-mail: m.elmoudane@gmail.com; El Maniani, M.; Sabbar, A.

2015-12-15

Highlights: • Results of ionic conductivities of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses. • Determination of glass transition temperature using DSC method. • Study of temperature and frequency on ionic conductivity of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses. - Abstract: Lithium–Lead–Bismuth phosphates glasses having, a composition 30Li{sub 3}PO{sub 4}–(70 − x)Pb{sub 3}(PO{sub 4}){sub 2}–xBiPO{sub 4} (45 ≤ x ≤ 60 mol%) were prepared by using the melt quenching method 1000 °C. The thermal stability of theses glasses increases with the substitution of Bi{sub 2}O{sub 3} with PbO. The ionic conductivity of all compositions havemore » been measured over a wide temperature (200–500 °C) and frequency range (1–106 Hz). The ionic conductivity data below and above T{sub g} follows Arrhenius and Vogel–Tamman–Fulcher (VTF) relationship, respectively. The activation energies are estimated and discussed. The dependence in frequency of AC conductivity is found to obey Jonscher’s relation.« less

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids

NASA Astrophysics Data System (ADS)

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM). Electronic supplementary information (ESI) available: In situ image of PEDOT in [HMIm]FAP and in situ studies of PEDOT grown in [EMIm]TFSA and redox behavior of PEDOT. See DOI: 10.1039/c0nr00579g

Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks.

PubMed

Shen, Li; Wu, Hao Bin; Liu, Fang; Brosmer, Jonathan L; Shen, Gurong; Wang, Xiaofeng; Zink, Jeffrey I; Xiao, Qiangfeng; Cai, Mei; Wang, Ge; Lu, Yunfeng; Dunn, Bruce

2018-06-01

Solid-state electrolytes are the key to the development of lithium-based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid-state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal-organic frameworks (MOFs), which transforms the MOF scaffolds into ionic-channel analogs with lithium-ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid-state lithium-ion conducting electrolytes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 Responsive Imidazolium-Type Poly(Ionic Liquid) Gels.

PubMed

Zhang, Jing; Xu, Dan; Guo, Jiangna; Sun, Zhe; Qian, Wenjing; Zhang, Ye; Yan, Feng

2016-07-01

Poly(ionic liquid) (PIL) gels with CO2 stimulus responsiveness have been synthesized through the copolymerization of an imidazolium-type ionic liquid monomer with 2-(dimethyl amino) ethyl methacrylate. Upon bubbling with CO2 gas, the prepared PIL solution is converted to a transparent and stable gel, which can be turned back to the initial solution state after N2 bubbling. The reversible sol-gel phase transition behavior is proved by the reversible values of viscosity and ionic conductivity. The possible mechanism for such a reversible sol-gel phase transition is demonstrated by NMR, conductivity, and rheological measurements. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Water Dissolvable Electrolyte with an Ionic Liquid for Eco-Friendly Electronics.

PubMed

Yamada, Shunsuke; Toshiyoshi, Hiroshi

2018-06-21

A water-dissolvable electrolyte is developed by combining an ionic liquid (IL) with poly(vinyl alcohol) (PVA), which decays over time by contact with water. An IL generally consists of two species of ions (anion and cation), and forms an electrical double layer (EDL) of a large electrostatic capacitance due to the ions accumulated in the vicinity of a conductive electrode when voltage is applied. In a similar manner, the ionic gel developed in this work forms an EDL due to the ions suspended in the conjugated polymer network while maintaining the gel form. Test measurements show a large capacitance of 13 µF cm -2 within the potential window of the IL. The ionic gel shows an electrical conductance of 20 µS cm -1 due to the ionic conduction, which depends on the weight ratio of the IL with respect to the polymer. The developed ionic gel dissolves into water in 16 h. Potential application includes the electrolyte in disposable electronics such as distributed sensors and energy harvesters that are supposed to be harmless to environment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conductance valve and pressure-to-conductance transducer method and apparatus

DOEpatents

Schoeniger, Joseph S.; Cummings, Eric B.; Brennan, James S.

2005-01-18

A device for interrupting or throttling undesired ionic transport through a fluid network is disclosed. The device acts as a fluid valve by reversibly generating a fixed "bubble" in the conducting solvent solution carried by the network. The device comprises a porous hydrophobic structure filling a portion of a connecting channel within the network and optionally incorporates flow restrictor elements at either end of the porous structure that function as pressure isolation barriers, and a fluid reservoir connected to the region of the channel containing the porous structure. Also included is a pressure pump connected to the fluid reservoir. The device operates by causing the pump to vary the hydraulic pressure to a quantity of solvent solution held within the reservoir and porous structure. At high pressures, most or all of the pores of the structure are filled with conducting liquid so the ionic conductance is high. At lower pressures, only a fraction of the pores are filled with liquid, so ionic conductivity is lower. Below a threshold pressure, the porous structure contains only vapor, so there is no liquid conduction path. The device therefore effectively throttles ionic transport through the porous structure and acts as a "conductance valve" or "pressure-to-conductance" transducer within the network.

Electrical and electrochemical studies on sodium ion-based gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Isa, K. B. Md; Othman, L.; Hambali, D.; Osman, Z.

2017-09-01

Gel polymer electrolytes (GPEs) have captured great attention because of their unique properties such as good mechanical stability, high flexibility and high conductivity approachable to that of the liquid electrolytes. In this work, we have prepared sodium ion conducting gel polymer electrolyte (GPE) films consisting of polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) as a polymer host using the solution casting technique. Sodium trifluoromethane- sulfonate (NaCF3SO3) was used as an ionic salt and the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizing solvent. Impedance spectroscopy measurements were carried out to determine the ionic conductivity of the GPE films. The sample containing 20 wt.% of NaCF3SO3 salt exhibits the highest room temperature ionic conductivity of 2.50 × 10-3 S cm-1. The conductivity of the GPE films was found to depend on the salt concentration that added to the films. The ionic and cationic transference numbers of GPE films were estimated by DC polarization and the combination of AC and DC polarization method, respectively. The results had shown that both ionic and cationic transference numbers are consistent with the conductivity studies. The electrochemical stability of the GPE films was tested using linear sweep voltammetry (LSV) and the value of working voltage range appears to be high enough to be used as an electrolyte in sodium batteries. The cyclic voltammetry (CV) studies confirmed the sodium ion conduction in the GPE films.

Reconstruction of apparent orthotropic conductivity tensor image using magnetic resonance electrical impedance tomography

NASA Astrophysics Data System (ADS)

Sajib, Saurav Z. K.; Kim, Ji Eun; Jeong, Woo Chul; Kim, Hyung Joong; Kwon, Oh In; Woo, Eung Je

2015-03-01

Magnetic resonance electrical impedance tomography visualizes current density and/or conductivity distributions inside an electrically conductive object. Injecting currents into the imaging object along at least two different directions, induced magnetic flux density data can be measured using a magnetic resonance imaging scanner. Without rotating the object inside the scanner, we can measure only one component of the magnetic flux density denoted as Bz. Since the biological tissues such as skeletal muscle and brain white matter show strong anisotropic properties, the reconstruction of anisotropic conductivity tensor is indispensable for the accurate observations in the biological systems. In this paper, we propose a direct method to reconstruct an axial apparent orthotropic conductivity tensor by using multiple Bz data subject to multiple injection currents. To investigate the anisotropic conductivity properties, we first recover the internal current density from the measured Bz data. From the recovered internal current density and the curl-free condition of the electric field, we derive an over-determined matrix system for determining the internal absolute orthotropic conductivity tensor. The over-determined matrix system is designed to use a combination of two loops around each pixel. Numerical simulations and phantom experimental results demonstrate that the proposed algorithm stably determines the orthotropic conductivity tensor.

High through-plane thermal conduction of graphene nanoflake filled polymer composites melt-processed in an L-shape kinked tube.

PubMed

Jung, Haejong; Yu, Seunggun; Bae, Nam-Seok; Cho, Suk Man; Kim, Richard Hahnkee; Cho, Sung Hwan; Hwang, Ihn; Jeong, Beomjin; Ryu, Ji Su; Hwang, Junyeon; Hong, Soon Man; Koo, Chong Min; Park, Cheolmin

2015-07-22

Design of materials to be heat-conductive in a preferred direction is a crucial issue for efficient heat dissipation in systems using stacked devices. Here, we demonstrate a facile route to fabricate polymer composites with directional thermal conduction. Our method is based on control of the orientation of fillers with anisotropic heat conduction. Melt-compression of solution-cast poly(vinylidene fluoride) (PVDF) and graphene nanoflake (GNF) films in an L-shape kinked tube yielded a lightweight polymer composite with the surface normal of GNF preferentially aligned perpendicular to the melt-flow direction, giving rise to a directional thermal conductivity of approximately 10 W/mK at 25 vol % with an anisotropic thermal conduction ratio greater than six. The high directional thermal conduction was attributed to the two-dimensional planar shape of GNFs readily adaptable to the molten polymer flow, compared with highly entangled carbon nanotubes and three-dimensional graphite fillers. Furthermore, our composite with its density of approximately 1.5 g/cm(3) was mechanically stable, and its thermal performance was successfully preserved above 100 °C even after multiple heating and cooling cycles. The results indicate that the methodology using an L-shape kinked tube is a new way to achieve polymer composites with highly anisotropic thermal conduction.

Anisotropic thermal transport property of defect-free GaN

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

Ju, Wenjing; Zhou, Zhongyuan, E-mail: zyzhou@seu.edu.cn, E-mail: zywei@seu.edu.cn; Wei, Zhiyong, E-mail: zyzhou@seu.edu.cn, E-mail: zywei@seu.edu.cn

2016-06-15

Non-equilibrium molecular dynamics (MD) simulation is performed to calculate the thermal conductivity of defect-free GaN along three high-symmetry directions. It is found that the thermal conductivity along [001] direction is about 25% higher than that along [100] or [120] direction. The calculated phonon dispersion relation and iso-energy surface from lattice dynamics show that the difference of the sound speeds among the three high-symmetry directions is quite small for the same mode. However, the variation of phonon irradiation with direction is qualitatively consistent with that of the calculated thermal conductivity. Our results indicate that the anisotropic thermal conductivity may partly resultmore » from the phonons in the low-symmetry region of the first Brillouin zone due to phonon focus effects, even though the elastic properties along the three high-symmetry directions are nearly isotropic. Thus, the phonon irradiation is able to better describe the property of thermal conductivity as compared to the commonly used phonon dispersion relation. The present investigations uncover the physical origin of the anisotropic thermal conductivity in defect-free GaN, which would provide an important guide for optimizing the thermal management of GaN-based device.« less

Strong anisotropy effect in an iron-based superconductor CaFe0.882Co0.118AsF

NASA Astrophysics Data System (ADS)

Ma, Yonghui; Ji, Qiucheng; Hu, Kangkang; Gao, Bo; Li, Wei; Mu, Gang; Xie, Xiaoming

2017-07-01

The anisotropy of iron-based superconductors is much smaller than that of the cuprates and that predicted by theoretical calculations. A credible understanding for this experimental fact is still lacking up to now. Here we experimentally study the magnetic-field-angle dependence of electronic resistivity in the superconducting phase of an iron-based superconductor CaFe{}0.882Co{}0.118AsF, and find the strongest anisotropy effect of the upper critical field among the iron-based superconductors based on the framework of Ginzburg-Landau theory. The evidence of the energy band structure and charge density distribution from electronic structure calculations demonstrates that the observed strong anisotropic effect mainly comes from the strong ionic bonding in between the ions of Ca2+ and F-, which weakens the interlayer coupling between the layers of FeAs and CaF. This finding provides a significant insight into the nature of the experimentally-observed strong anisotropic effect of electronic resistivity, and also paves the way for designing exotic two-dimensional artificial unconventional superconductors in the future.

Highly Conductive Anion Exchange Block Copolymers

DTIC Science & Technology

We are developing a comprehensive fundamental understanding of the interplay between transport and morphology in newly synthesized hydroxide...conducting block copolymers. We are synthesizing hydroxide conducting block copolymers of various (1) morphology types, (2) ionic concentrations, and (3...ionic domain sizes. We are carefully characterizing the morphology and transport properties using both conventional and new advanced in situ techniques

Overview of thermal conductivity models of anisotropic thermal insulation materials

NASA Astrophysics Data System (ADS)

Skurikhin, A. V.; Kostanovsky, A. V.

2017-11-01

Currently, the most of existing materials and substances under elaboration are anisotropic. It makes certain difficulties in the study of heat transfer process. Thermal conductivity of the materials can be characterized by tensor of the second order. Also, the parallelism between the temperature gradient vector and the density of heat flow vector is violated in anisotropic thermal insulation materials (TIM). One of the most famous TIM is a family of integrated thermal insulation refractory material («ITIRM»). The main component ensuring its properties is the «inflated» vermiculite. Natural mineral vermiculite is ground into powder state, fired by gas burner for dehydration, and its precipitate is then compressed. The key feature of thus treated batch of vermiculite is a package structure. The properties of the material lead to a slow heating of manufactured products due to low absorption and high radiation reflection. The maximum of reflection function is referred to infrared spectral region. A review of current models of heat propagation in anisotropic thermal insulation materials is carried out, as well as analysis of their thermal and optical properties. A theoretical model, which allows to determine the heat conductivity «ITIRM», can be useful in the study of thermal characteristics such as specific heat capacity, temperature conductivity, and others. Materials as «ITIRM» can be used in the metallurgy industry, thermal energy and nuclear power-engineering.

Nanoscale Ionic Liquids

DTIC Science & Technology

2006-11-01

Technical Report 11 December 2005 - 30 November 2006 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Nanoscale Ionic Liquids 5b. GRANT NUMBER FA9550-06-1-0012...Title: Nanoscale Ionic Liquids Principal Investigator: Emmanuel P. Giannelis Address: Materials Science and Engineering, Bard Hall, Cornell University...based fluids exhibit high ionic conductivity. The NFs are typically synthesized by grafting a charged, oligomeric corona onto the nanoparticle cores

Terahertz Investigations of Extraordinarily Efficient Conduction in a Redox Active Ionic Liquid.

NASA Astrophysics Data System (ADS)

Thorsmolle, Verner; Brauer, Jan; Rothenberger, Guido; Kuang, Daibin; Zakeeruddin, Shaik; Grätzel, Michael; Moser, Jacques

2009-03-01

Iodine added to iodide-based ionic liquids leads to extraordinarily efficient charge transport, vastly exceeding expectancy for such viscous systems. Using terahertz time-domain spectroscopy, in conjunction with dc conductivity and viscosity measurements we unravel the conductivity pathways in 1-methyl-3-propylimidazolium iodide melts. Applying low temperatures, we demonstrate for the first time conduction entirely due to a Grotthus bond-exchange mechanism at iodine concentrations higher than 3.9 M. The terahertz and transport results are reconciled in a model providing a quantitative description of the conduction by physical diffusion and the Grotthus bond-exchange process. These novel results are of great importance for the fundamental understanding of conduction in molten salts and for applications where ionic liquids are used as charge-transporting media such as in batteries and dye-sensitized solar cells.

[Advances of poly (ionic liquid) materials in separation science].

PubMed

Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

2015-11-01

Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials.

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

Casimir forces on a bi-anisotropic absorbing magneto-dielectric slab between two parallel conducting plates

NASA Astrophysics Data System (ADS)

Amooshahi, Majid; Shoughi, Ali

2018-05-01

A fully canonical quantization of electromagnetic field in the presence of a bi-anisotropic absorbing magneto-dielectric slab is demonstrated. The electric and the magnetic polarization densities of the magneto-dielectric slab are defined in terms of the dynamical variables modeling the slab and the coupling tensors that couple the electromagnetic field to the slab. The four susceptibility tensors of the bi-anisotropic magneto-dielectric slab are expressed in terms of the coupling tensors that couple an electromagnetic field to the slab. It is shown that the four susceptibility tensors of the bi-anisotropic magneto-dielectric slab satisfy Kramers-Kronig relations. The Maxwell’s equations are exactly solved in the presence of the bi-anisotropic magneto-dielectric slab. The tangential and the normal components of the Casimir forces exerted on the bi-anisotropic magnet-dielectric slab exactly are calculated in the vacuum state and thermal state of the total system. It is shown that the tangential components of the Casimir forces vanish when the bi-anisotropic slab is converted to an isotropic slab.

Structural control of mixed ionic and electronic transport in conducting polymers

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

Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. Wemore » quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. As a result, these findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.« less

First-principles investigations of ionic conduction in Li and Na borohydrides

NASA Astrophysics Data System (ADS)

Varley, Joel; Heo, Tae-Wook; Ray, Keith; Bonev, Stanimir; Wood, Brandon

Recent experimental studies have identified a family of alkali borohydride materials that exhibit superionic transition temperatures approaching room temperature and ionic conductivities exceeding 0.1 S/cm-1, making them highly promising solid electrolytes for next-generation batteries. Despite the rapid advances in improving the superionic conductivity in these materials, an understanding of the exact mechanisms driving the transport remains unknown. Here we use ab initio molecular dynamics calculations to address this issue by characterizing the diffusivity of the Li and Na species in a representative set of closoborane ionic conductors. We investigate both the Na and Li-containing borohydrides with icosahedral (B12H12) and double-capped square antiprism (B10H10) anion species and discuss the trends in ionic conductivity as a function of stoichiometry and the incorporation of various dopants. Our results support the borohydrides as a subset of a larger family of very promising solid electrolytes and identify strategies to improving the conductivity in these materials. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Structural control of mixed ionic and electronic transport in conducting polymers

DOE PAGES

Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.; ...

2016-04-19

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. Wemore » quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. As a result, these findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.« less

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

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

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Intercalated hybrid of kaolinite with KH2PO4 showing high ionic conductivity (∼10-4 S cm-1) at room temperature

NASA Astrophysics Data System (ADS)

Liu, Shao-Xian; Xue, Chen; Yang, Hao; Huang, Xiao-Qing; Zou, Yang; Ding, Yan-Ni; Li, Li; Ren, Xiao-Ming

2017-12-01

In this paper, we present the study of preparation and ionic conductance for an intercalated hybrid of kaolinite with potassium dihydrogen. The intercalation efficiency is high up to ca. 90%. The intercalated hybrid has been characterized by powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The ionic conductivity (σ) of the hybrid material is strongly dependent on the moisture in the environment, with σ = 8.4 × 10-10 S cm-1 at 293 K and gradually increases to 7.16 × 10-9 S cm-1 under N2 atmosphere (anhydrous environment) at 353 K as well as an activation energy of Ea = 0.618 e V, whereas σ = 2.19 × 10-4 S cm-1 at 100% relative humidity and 293 K with Ea = 0.44 eV. The mechanism that the moisture affects the ionic conductance of the intercalated hybrid is further discussed.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE PAGES

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.; ...

2015-07-10

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions.

PubMed

Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong

2010-10-05

Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes

PubMed Central

2015-01-01

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials. PMID:27162971

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects

PubMed Central

Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-01-01

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

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

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody

2016-06-15

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providingmore » flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.« less

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

NASA Astrophysics Data System (ADS)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

2016-06-01

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

Ion Conduction in Perfectly Aligned Block Copolymer-Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Elabd, Yossef A.; Winey, Karen I.

2011-03-01

Our earlier work to correlate the transport measurements in diblock copolymer-ionic liquid mixtures was limited by our bulk samples that have only partial alignment. Here, thin films with perfect alignment of lamellar microdomains from mixtures of a poly(methyl methacrylate- b -styrene) diblock copolymer and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, have been studied. The morphologies will be characterized by cross-sectional transmission electron microscopy. Ion conduction will be presented within and through the thin film.

Graphene Oxide Papers Simultaneously Doped with Mg(2+) and Cl(-) for Exceptional Mechanical, Electrical, and Dielectric Properties.

PubMed

Lin, Xiuyi; Shen, Xi; Sun, Xinying; Liu, Xu; Wu, Ying; Wang, Zhenyu; Kim, Jang-Kyo

2016-01-27

This paper reports simultaneous modification of graphene oxide (GO) papers by functionalization with MgCl2. The Mg(2+) ions enhance both the interlayer cross-links and lateral bridging between the edges of adjacent GO sheets by forming Mg-O bonds. The improved load transfer between the GO sheets gives rise to a maximum of 200 and 400% increases in Young's modulus and tensile strength of GO papers. The intercalation of chlorine between the GO layers alters the properties of GO papers in two ways by forming ionic Cl(-) and covalent C-Cl bonds. The p-doping effect arising from Cl contributes to large enhancements in electrical conductivities of GO papers, with a remarkable 2500-fold surge in the through-thickness direction. The layered structure and the anisotropic electrical conductivities of reduced GO papers naturally create numerous nanocapacitors that lead to charge accumulation based on the Maxwell-Wagner (MW) polarization. The combined effect of much promoted dipolar polarizations due to Mg-O, C-Cl, and Cl(-) species results in an exceptionally high dielectric constant greater than 60 000 and a dielectric loss of 3 at 1 kHz by doping with 2 mM MgCl2. The excellent mechanical and electrical properties along with unique dielectric performance shown by the modified GO and rGO papers open new avenues for niche applications, such as electromagnetic interference shielding materials.

Novel Mg-Doped SrMoO3 Perovskites Designed as Anode Materials for Solid Oxide Fuel Cells

PubMed Central

Cascos, Vanessa; Alonso, José Antonio; Fernández-Díaz, María Teresa

2016-01-01

SrMo1−xMxO3−δ (M = Fe and Cr, x = 0.1 and 0.2) oxides have been recently described as excellent anode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFC) with LSGM as the electrolyte. In this work, we have improved their properties by doping with aliovalent Mg ions at the B-site of the parent SrMoO3 perovskite. SrMo1−xMgxO3−δ (x = 0.1, 0.2) oxides have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers near 900 mW/cm−2 at 850 °C using pure H2 as fuel. We have studied its crystal structure with an “in situ” neutron power diffraction (NPD) experiment at temperatures as high as 800 °C, emulating the working conditions of an SOFC. Adequately high oxygen deficiencies, observed by NPD, together with elevated disk-shaped anisotropic displacement factors suggest a high ionic conductivity at the working temperatures. Furthermore, thermal expansion measurements, chemical compatibility with the LSGM electrolyte, electronic conductivity and reversibility upon cycling in oxidizing-reducing atmospheres have been carried out to find out the correlation between the excellent performance as an anode and the structural features. PMID:28773708

Specialist gelator for ionic liquids.

PubMed

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

2005-11-08

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

Thermal load leveling during silicon crystal growth from a melt using anisotropic materials

DOEpatents

Carlson, Frederick M.; Helenbrook, Brian T.

2016-10-11

An apparatus for growing a silicon crystal substrate comprising a heat source, an anisotropic thermal load leveling component, a crucible, and a cold plate component is disclosed. The anisotropic thermal load leveling component possesses a high thermal conductivity and may be positioned atop the heat source to be operative to even-out temperature and heat flux variations emanating from the heat source. The crucible may be operative to contain molten silicon in which the top surface of the molten silicon may be defined as a growth interface. The crucible may be substantially surrounded by the anisotropic thermal load leveling component. The cold plate component may be positioned above the crucible to be operative with the anisotropic thermal load leveling component and heat source to maintain a uniform heat flux at the growth surface of the molten silicon.

Quark–gluon plasma phenomenology from anisotropic lattice QCD

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

Skullerud, Jon-Ivar; Kelly, Aoife; Aarts, Gert

The FASTSUM collaboration has been carrying out simulations of N{sub f} = 2 + 1 QCD at nonzero temperature in the fixed-scale approach using anisotropic lattices. Here we present the status of these studies, including recent results for electrical conductivity and charge diffusion, and heavy quarkonium (charm and beauty) physics.

Computational modeling of the structure and the ionic conductivity of the solid electrolyte materials Li3AsS4 and its Ge substitutions

NASA Astrophysics Data System (ADS)

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

Oak Ridge National Laboratory (G. Sahu et al.) reported that the substitution of Ge into Li3AsS4 leads to the composition Li3.334Ge0.334As0.666S4 with impressively high ionic conductivity . We use ab initio calculations to examine the structural relationships and the ionic conductivity mechanisms for pure Li3AsS4, Li3.334Ge0.334As0.666S4, and other compositions of these electrolytes. Supported by NSF Grant DMR-1105485 and 1507942 and WFU's DEAC cluster.

Temperature dependence of electrical conduction in PEMA-EMITFSI film

NASA Astrophysics Data System (ADS)

Zain, N. F.; Megat Hasnan, M. M. I.; Sabri, M. F. M.; Said, S. M.; Mohamed, N. S.; Salleh, F.

2018-04-01

Transparent and flexible film of poly (ethyl methacrylate) incorporated with 1-ethyl-3-methyl imidazolium bis(trifluorosulfonyl) imide ionic liquid (PEMA-EMITFSI) with thickness between 100 and 200 µm was fabricated by using solution casting technique. From the ionic transport measurement, it is confirmed that the electrical conduction in PEMA-EMITFSI film is mainly contributed by ionic transport. Moreover, the temperature-dependence of electrical conductivity measurement for 7 days reveals that the electrical properties of PEMA-EMITFSI film could be able to withstand a number of thermal cycles and be lasting for a period of time for potentially used as thermoelectric material through thermal heating.

Synthesis, structure, and ionic conductivity of solid solution, Li10+δM1+δP2-δS12 (M = Si, Sn).

PubMed

Hori, Satoshi; Suzuki, Kota; Hirayama, Masaaki; Kato, Yuki; Saito, Toshiya; Yonemura, Masao; Kanno, Ryoji

2014-01-01

Solid solutions of the silicon and tin analogous phases of the superionic conductor Li(10)MP(2)S(12) (M = Si, Sn) were synthesized by a conventional solid-state reaction in an evacuated silica tube at 823 K. The ranges of the solid solutions were determined to be 0.20 < δ < 0.43 and -0.25 < δ < -0.01 in Li(10+δ)M(1+δ)P(2-δ)S(12) (0.525 ≤k≤ 0.60 and 0.67 ≤k≤ 0.75 in Li(4-k)M(1-k)PkS(4)) for the Si and Sn systems, respectively. The ionic conductivity of these systems varied as a function of the changing M ions: the Si and Sn systems showed lower conductivity than the Ge system, Li(10+δ)Ge(1+δ)P(2-δ)S(12). The conductivity change for different elements might be due to the lattice size and lithium content affecting the ionic conduction. The relationship between ionic conduction, structure, and lithium concentration is discussed based on the structural and electrochemical information for the silicon, germanium, and tin systems.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

PubMed

Choi, Bong Gill; Hong, Jinkee; Park, Young Chul; Jung, Doo Hwan; Hong, Won Hi; Hammond, Paula T; Park, Hoseok

2011-06-28

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters. The functionalized graphenes controlled the state of water by means of nanoscale manipulation of the physical geometry and chemical functionality of ionic channels. Furthermore, the confinement of bound water within the reorganized nanochannels of composite membranes was confirmed by the enhanced proton conductivity at high temperature and the low activation energy for ionic conduction through a Grotthus-type mechanism. The selectively facilitated transport behavior of composite membranes such as high proton conductivity and low methanol crossover was attributed to the confined bound water, resulting in high-performance fuel cells.

A Quaternary Sodium Superionic Conductor - Na 10.8Sn 1.9PS 11.8

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

Yu, Zhaoxin; Shang, Shun -Li; Gao, Yue

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8Sn 1.9PS 11.8, exhibiting a high ionic conductivity of 0.67 mS cm –1 at 25 °C. This high ionic conductivity originates from the presence ofmore » a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. In conclusion, the Na 10.8Sn 1.9PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.« less

A Quaternary Sodium Superionic Conductor - Na 10.8Sn 1.9PS 11.8

DOE PAGES

Yu, Zhaoxin; Shang, Shun -Li; Gao, Yue; ...

2018-01-31

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8Sn 1.9PS 11.8, exhibiting a high ionic conductivity of 0.67 mS cm –1 at 25 °C. This high ionic conductivity originates from the presence ofmore » a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. In conclusion, the Na 10.8Sn 1.9PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.« less

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Klinkenberg effect in hydrodynamics of gas flow through anisotropic porous materials

NASA Astrophysics Data System (ADS)

Wałowski, Grzegorz; Filipczak, Gabriel

2017-10-01

This study discusses results of experiments on hydrodynamic assessment of gas flow through backbone (skeletal) porous materials with an anisotropic structure. The research was conducted upon materials of diversified petrographic characteristics, both natural origin (rocky, pumice) and process materials (char and coke). The study was conducted for a variety of hydrodynamic conditions, using air, as well as for nitrogen and carbon dioxide. The basis for assessing hydrodynamics of gas flow through porous material was a gas stream that results from the pressure forcing such flow. The results of measurements indicate a clear impact of the type of material on the gas permeability, and additionally - as a result of their anisotropic internal structure - to a significant effect of the flow direction on the value of gas stream.

New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

DOE PAGES

Fang, Youxing; Jiang, Xueguang; Dai, Sheng; ...

2015-07-14

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10 -4 S cm -1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

High Current Ionic Diode Using Homogeneously Charged Asymmetric Nanochannel Network Membrane.

PubMed

Choi, Eunpyo; Wang, Cong; Chang, Gyu Tae; Park, Jungyul

2016-04-13

A high current ionic diode is achieved using an asymmetric nanochannel network membrane (NCNM) constructed by soft lithography and in situ self-assembly of nanoparticles with uniform surface charge. The asymmetric NCNM exhibits high rectified currents without losing a rectification ratio because of its ionic selectivity gradient and differentiated electrical conductance. Asymmetric ionic transport is analyzed with diode-like I-V curves and visualized via fluorescent dyes, which is closely correlated with ionic selectivity and ion distribution according to variation of NCNM geometries.

New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

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

Fang, Youxing; Jiang, Xueguang; Dai, Sheng

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10 -4 S cm -1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

Resolution of anisotropic and shielded highly conductive layers using 2-D electromagnetic modelling in the Rhine Graben and Black Forest

NASA Astrophysics Data System (ADS)

Tezkan, Bülent; Červ, Václav; Pek, Josef

1992-12-01

Anisotropy in magnetotelluric (MT) data has been found very often and has been explained as the result of local structures of different conductivities. In this paper, an observed anisotropy in MT data is not interpreted qualitatively in terms of local structures but is modelled quantitatively by a quasi-anisotropic layer. Besides the MT transfer functions, measurements of the vertical magnetic component are required. The second goal of this paper is to describe a method which permits the resolution of mid-crustal conductive layers in the presence of an additional high-conductivity layer at the surface. This method is possible in a two-dimensional (2-D) situation that limits the spatial extension of the surface structure. Again, vertical magnetic field recordings are necessary, but the phase of the E-polarization with respect to the 2-D structure is the most sensitive parameter. Using two field sites in Southern Germany, it has been possible to give a quantitative explanation of anisotropy and an improved depth resolution, and to derive an integrated conductivity of the highly conductive mid-crustal layers using MT and geomagnetic depth sounding data. The anisotropic highly conductive layer is located 12 km beneath the poorly conductive Black Forest crystalline rocks, whereas it is at a depth of 6 km beneath the highly conductive Rhine Graben sediments.

Mg2B2O5 Nanowire Enabled Multifunctional Solid-State Electrolytes with High Ionic Conductivity, Excellent Mechanical Properties, and Flame-Retardant Performance.

PubMed

Sheng, Ouwei; Jin, Chengbin; Luo, Jianmin; Yuan, Huadong; Huang, Hui; Gan, Yongping; Zhang, Jun; Xia, Yang; Liang, Chu; Zhang, Wenkui; Tao, Xinyong

2018-05-09

High ionic conductivity, satisfactory mechanical properties, and wide electrochemical windows are crucial factors for composite electrolytes employed in solid-state lithium-ion batteries (SSLIBs). Based on these considerations, we fabricate Mg 2 B 2 O 5 nanowire enabled poly(ethylene oxide) (PEO)-based solid-state electrolytes (SSEs). Notably, these SSEs have enhanced ionic conductivity and a large electrochemical window. The elevated ionic conductivity is attributed to the improved motion of PEO chains and the increased Li migrating pathway on the interface between Mg 2 B 2 O 5 and PEO-LiTFSI. Moreover, the interaction between Mg 2 B 2 O 5 and -SO 2 - in TFSI - anions could also benefit the improvement of conductivity. In addition, the SSEs containing Mg 2 B 2 O 5 nanowires exhibit improved the mechanical properties and flame-retardant performance, which are all superior to the pristine PEO-LiTFSI electrolyte. When these multifunctional SSEs are paired with LiFePO 4 cathodes and lithium metal anodes, the SSLIBs show better rate performance and higher cyclic capacity of 150, 106, and 50 mAh g -1 under 0.2 C at 50, 40, and 30 °C. This strategy of employing Mg 2 B 2 O 5 nanowires provides the design guidelines of assembling multifunctional SSLIBs with high ionic conductivity, excellent mechanical properties, and flame-retardant performance at the same time.

Solid state ionics: a Japan perspective

PubMed Central

Yamamoto, Osamu

2017-01-01

Abstract The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term ‘solid state ionics’ was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1–xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm–1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm–1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology. PMID:28804526

Effect of SiO2 addition and gamma irradiation on the lithium borate glasses

NASA Astrophysics Data System (ADS)

Raut, A. P.; Deshpande, V. K.

2018-01-01

The physical properties like density, glass transition temperature (Tg), and ionic conductivity of lithium borate (LB) glasses with SiO2 addition were measured before and after gamma irradiation. Remarkable changes in properties have been obtained in the physical properties of LB glasses with SiO2 addition and after gamma irradiation. The increase in density and glass transition temperature of LB glasses with SiO2 addition has been explained with the help of increase in density of cross linking due to SiO4 tetrahedra formation. The increase in ionic conductivity with SiO2 addition was explained with the help of ‘mixed glass former effect’. The increase in density and Tg of LB glasses with SiO2 addition after gamma irradiation has been attributed to fragmentation of bigger ring structure into smaller rings, which increases the density of cross linking and hence compaction. The exposure of gamma irradiation has lead to decrease in ionic conductivity of LB glasses with SiO2 addition. The atomic displacement caused by gamma irradiation resulted in filling of interstices and decrease in trapping sites. This explains the obtained decrease in ionic conductivity after gamma irradiation of glasses. The obtained results of effect of SiO2 addition and gamma irradiation on the density, Tg and ionic conductivity has been supported by FTIR results.

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Polymerized Paired Ions as Polymeric Ionic Liquid-Proton Conductivity.

PubMed

Gu, Hong; Yan, Feng; Texter, John

2016-07-01

A new polymerized ionic liquid has been derived by photopolymerization of a stimuli-responsive ionic liquid surfactant, ILAMPS, which is composed of polymerizable, paired ions. The cation is 1-methyl-3-[11-(acryloyloxy)undecyl] imidazolium (IL), and the anion is 2-acrylamido-2-methyl-1-propanesulfonate (AMPS). This ion combination is a new ionic liquid. The resulting hygroscopic resins are highly polarizable, suitable for sensor design and for ultracapacitor fabrication and proton conducting. Interactions of imidazolium with anions provide basis for stimuli-responsiveness, and are used to promote proton transport. Doping with one equivalent of HPF6 at 0% relative humidity produces a 100-fold increase in proton conductivity at 100-125 °C and activation energies for proton transport lower than those of Nafion at water loadings less than 5 per sulfonate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Polarized Spectroscopy to Investigate Order in Thin-Films of Ionic Self-Assembled Materials Based on Azo-Dyes

PubMed Central

Ahmad, Mariam; Andersen, Frederik; Brend Bech, Ári; Bendixen, H. Krestian L.; Nawrocki, Patrick R.; Bloch, Anders J.; Bora, Ilkay; Bukhari, Tahreem A.; Bærentsen, Nicolai V.; Carstensen, Jens; Chima, Smeeah; Colberg, Helene; Dahm, Rasmus T.; Daniels, Joshua A.; Dinckan, Nermin; El Idrissi, Mohamed; Erlandsen, Ricci; Førster, Marc; Ghauri, Yasmin; Gold, Mikkel; Hansen, Andreas; Hansen, Kenn; Helmsøe-Zinck, Mathias; Henriksen, Mathias; Hoffmann, Sophus V.; Hyllested, Louise O. H.; Jensen, Casper; Kallenbach, Amalie S.; Kaur, Kirandip; Khan, Suheb R.; Kjær, Emil T. S.; Kristiansen, Bjørn; Langvad, Sylvester; Lund, Philip M.; Munk, Chastine F.; Møller, Theis; Nehme, Ola M. Z.; Nejrup, Mathilde Rove; Nexø, Louise; Nielsen, Simon Skødt Holm; Niemeier, Nicolai; Nikolajsen, Lasse V.; Nøhr, Peter C. T.; Skaarup Ovesen, Jacob; Paustian, Lucas; Pedersen, Adam S.; Petersen, Mathias K.; Poulsen, Camilla M.; Praeger-Jahnsen, Louis; Qureshi, L. Sonia; Schiermacher, Louise S.; Simris, Martin B.; Smith, Gorm; Smith, Heidi N.; Sonne, Alexander K.; Zenulovic, Marko R.; Winther Sørensen, Alma; Vogt, Emil; Væring, Andreas; Westermann, Jonas; Özcan, Sevin B.

2018-01-01

Three series of ionic self-assembled materials based on anionic azo-dyes and cationic benzalkonium surfactants were synthesized and thin films were prepared by spin-casting. These thin films appear isotropic when investigated with polarized optical microscopy, although they are highly anisotropic. Here, three series of homologous materials were studied to rationalize this observation. Investigating thin films of ordered molecular materials relies to a large extent on advanced experimental methods and large research infrastructure. A statement that in particular is true for thin films with nanoscopic order, where X-ray reflectometry, X-ray and neutron scattering, electron microscopy and atom force microscopy (AFM) has to be used to elucidate film morphology and the underlying molecular structure. Here, the thin films were investigated using AFM, optical microscopy and polarized absorption spectroscopy. It was shown that by using numerical method for treating the polarized absorption spectroscopy data, the molecular structure can be elucidated. Further, it was shown that polarized optical spectroscopy is a general tool that allows determination of the molecular order in thin films. Finally, it was found that full control of thermal history and rigorous control of the ionic self-assembly conditions are required to reproducibly make these materials of high nanoscopic order. Similarly, the conditions for spin-casting are shown to be determining for the overall thin film morphology, while molecular order is maintained. PMID:29462883

Using Polarized Spectroscopy to Investigate Order in Thin-Films of Ionic Self-Assembled Materials Based on Azo-Dyes.

PubMed

Kühnel, Miguel R Carro-Temboury Martin; Ahmad, Mariam; Andersen, Frederik; Bech, Ári Brend; Bendixen, H Krestian L; Nawrocki, Patrick R; Bloch, Anders J; Bora, Ilkay; Bukhari, Tahreem A; Bærentsen, Nicolai V; Carstensen, Jens; Chima, Smeeah; Colberg, Helene; Dahm, Rasmus T; Daniels, Joshua A; Dinckan, Nermin; Idrissi, Mohamed El; Erlandsen, Ricci; Førster, Marc; Ghauri, Yasmin; Gold, Mikkel; Hansen, Andreas; Hansen, Kenn; Helmsøe-Zinck, Mathias; Henriksen, Mathias; Hoffmann, Sophus V; Hyllested, Louise O H; Jensen, Casper; Kallenbach, Amalie S; Kaur, Kirandip; Khan, Suheb R; Kjær, Emil T S; Kristiansen, Bjørn; Langvad, Sylvester; Lund, Philip M; Munk, Chastine F; Møller, Theis; Nehme, Ola M Z; Nejrup, Mathilde Rove; Nexø, Louise; Nielsen, Simon Skødt Holm; Niemeier, Nicolai; Nikolajsen, Lasse V; Nøhr, Peter C T; Orlowski, Dominik B; Overgaard, Marc; Ovesen, Jacob Skaarup; Paustian, Lucas; Pedersen, Adam S; Petersen, Mathias K; Poulsen, Camilla M; Praeger-Jahnsen, Louis; Qureshi, L Sonia; Ree, Nicolai; Schiermacher, Louise S; Simris, Martin B; Smith, Gorm; Smith, Heidi N; Sonne, Alexander K; Zenulovic, Marko R; Sørensen, Alma Winther; Sørensen, Karina; Vogt, Emil; Væring, Andreas; Westermann, Jonas; Özcan, Sevin B; Sørensen, Thomas Just

2018-02-15

Three series of ionic self-assembled materials based on anionic azo-dyes and cationic benzalkonium surfactants were synthesized and thin films were prepared by spin-casting. These thin films appear isotropic when investigated with polarized optical microscopy, although they are highly anisotropic. Here, three series of homologous materials were studied to rationalize this observation. Investigating thin films of ordered molecular materials relies to a large extent on advanced experimental methods and large research infrastructure. A statement that in particular is true for thin films with nanoscopic order, where X-ray reflectometry, X-ray and neutron scattering, electron microscopy and atom force microscopy (AFM) has to be used to elucidate film morphology and the underlying molecular structure. Here, the thin films were investigated using AFM, optical microscopy and polarized absorption spectroscopy. It was shown that by using numerical method for treating the polarized absorption spectroscopy data, the molecular structure can be elucidated. Further, it was shown that polarized optical spectroscopy is a general tool that allows determination of the molecular order in thin films. Finally, it was found that full control of thermal history and rigorous control of the ionic self-assembly conditions are required to reproducibly make these materials of high nanoscopic order. Similarly, the conditions for spin-casting are shown to be determining for the overall thin film morphology, while molecular order is maintained.

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

Increasing Black Hole Feedback-induced Quenching with Anisotropic Thermal Conduction

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

Kannan, Rahul; Vogelsberger, Mark; Pfrommer, Christoph

Feedback from central supermassive black holes is often invoked to explain the low star formation rates (SFRs) in the massive galaxies at the centers of galaxy clusters. However, the detailed physics of the coupling of the injected feedback energy with the intracluster medium (ICM) is still unclear. Using high-resolution magnetohydrodynamic cosmological simulations of galaxy cluster formation, we investigate the role of anisotropic thermal conduction in shaping the thermodynamic structure of clusters, and in particular, in modifying the impact of black hole feedback. Stratified anisotropically conducting plasmas are formally always unstable, and thus more prone to mixing, an expectation borne outmore » by our results. The increased mixing efficiently isotropizes the injected feedback energy, which in turn significantly improves the coupling between the feedback energy and the ICM. This facilitates an earlier disruption of the cool-core, reduces the SFR by more than an order of magnitude, and results in earlier quenching despite an overall lower amount of feedback energy injected into the cluster core. With conduction, the metallicity gradients and dispersions are lowered, aligning them better with observational constraints. These results highlight the important role of thermal conduction in establishing and maintaining the quiescence of massive galaxies.« less

Conductivity relaxation and charge transport of trihexyl tetradecyl phosphonium dicyanamide ionic liquid by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Thasneema K., K.; Thayyil, M. Shahin; Krishna Kumar N., S.; Govindaraj, G.; Saheer, V. C.

2018-04-01

Usually ionic liquids consists of a large organic cation with low symmetry such as imidazolium, pyridinium, quaternary ammonium or phosponium etc combined with enormously wide range of inorganic or organic symmetric anion with melting point below 100. Ionic liquids existing in an extremely large number of possible ion pair combinations. It offers a very wide range of thermo physical properties led to the concept of designer solvents for specific applications. Due to the features of high chemical and thermal stability, low vapor pressure non flammability high ionic conductivity, and they show a good solvent ability towards a great variety of organic or inorganic compounds, ionic liquids have a widespread use in many areas such as batteries, fuel cell, solar cells, super capacitors etc. The main focus of this work is the study of molecular dynamics and conductivity relaxation of amorphous Trihexyl tetradecyl phosphonium dicyanamide ([P14,6,6,6][N(CN)2]) ionic liquid which is proved as a better electrolyte in super capacitors, over a wide frequency 10-2 Hz to 107 Hz and the temperature range between 123k and 265 k by means of Broadband Dielectric Spectroscopy. We observe alpha conductivity relaxation and secondary relaxation above and below Glass Transition Temperature. The experimental results were analyzed using electric modulus representation. The analysis emphasis the inter molecular interaction and the nature of glass forming system, whether it is fragile or strong system. The ionic liquid shows a fragile behavior and the fragility index m=123.59. TGA result of the sample exhibit a good resistance to thermal decomposition, up to 300°C.

Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

PubMed

Reddy, Th Dhileep N; Mallik, Bhabani S

2017-04-19

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

Interaction potentials of anisotropic nanocrystals from the trajectory sampling of particle motion using in situ liquid phase transmission electron microscopy

DOE PAGES

Chen, Qian; Cho, Hoduk; Manthiram, Karthish; ...

2015-03-23

We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power ofmore » this approach to reveal unanticipated features of nanocrystal–nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics.« less

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

NASA Astrophysics Data System (ADS)

Widanarto, W.; Ramdhan, A. M.; Ghoshal, S. K.; Effendi, M.; Cahyanto, W. T.; Warsito

An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO2·xLi2O·15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800 °C followed by thermal annealing at 320 °C for 3 h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6), monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4 × 10-7 S cm-1 at the frequency of 54 Hz and in the temperature range of 323-473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.

Electrochemical and diffusional insights of combustion synthesized SrLi2Ti6O14 negative insertion material for Li-ion Batteries

NASA Astrophysics Data System (ADS)

Dayamani, Allumolu; Shinde, Ganesh S.; Chaupatnaik, Anshuman; Rao, R. Prasada; Adams, Stefan; Barpanda, Prabeer

2018-05-01

Solvothermal synthetic routes can provide energy-savvy platforms to fabricate battery anode materials involving relatively milder annealing steps vis-à-vis the conventional solid-state synthesis. These energy efficient routes in turn restrict aggressive grain growth to form nanoscale particles favouring efficient Li+ diffusion. Here, we report an economic solution combustion synthesis of SrLi2Ti6O14 anode involving nitrate-urea complexation with a short annealing duration of only 2 h (900 °C). Rietveld refinement confirms the phase purity of target product assuming an orthorhombic framework (Cmca symmetry). It delivers reversible capacity of ∼125 mAh.g-1 at a rate of C/20 involving a 1.38 V Ti4+/Ti3+ redox activity with excellent rate kinetics and cycling stability. Bond valence site energy (BVSE) calculations gauge SrLi2Ti6O14 to be an anisotropic 3D Li+ ion conductor with the highest ionic conductivity along the c direction. The electrochemical and diffusional pathways have been elucidated for combustion prepared SrLi2Ti6O14 as an efficient and safe negative electrode candidate for Li-ion batteries.

Electrical wave propagation in an anisotropic model of the left ventricle based on analytical description of cardiac architecture.

PubMed

Pravdin, Sergey F; Dierckx, Hans; Katsnelson, Leonid B; Solovyova, Olga; Markhasin, Vladimir S; Panfilov, Alexander V

2014-01-01

We develop a numerical approach based on our recent analytical model of fiber structure in the left ventricle of the human heart. A special curvilinear coordinate system is proposed to analytically include realistic ventricular shape and myofiber directions. With this anatomical model, electrophysiological simulations can be performed on a rectangular coordinate grid. We apply our method to study the effect of fiber rotation and electrical anisotropy of cardiac tissue (i.e., the ratio of the conductivity coefficients along and across the myocardial fibers) on wave propagation using the ten Tusscher-Panfilov (2006) ionic model for human ventricular cells. We show that fiber rotation increases the speed of cardiac activation and attenuates the effects of anisotropy. Our results show that the fiber rotation in the heart is an important factor underlying cardiac excitation. We also study scroll wave dynamics in our model and show the drift of a scroll wave filament whose velocity depends non-monotonically on the fiber rotation angle; the period of scroll wave rotation decreases with an increase of the fiber rotation angle; an increase in anisotropy may cause the breakup of a scroll wave, similar to the mother rotor mechanism of ventricular fibrillation.

Electronic, optical, infrared, and elastic properties of KCdCO3F from first principles

NASA Astrophysics Data System (ADS)

Huang, Xue-Qian; Xue, Han-Yu; Zhang, Can; Pang, Dong-Dong; Lv, Zhen-Long; Duan, Man-Yi

2018-05-01

KCdCO3F is a newly synthesized promising ultraviolet nonlinear optical crystal, but its structure is disputed and its fundamental properties have not been well studied. Here our first-principles study indicates that the structure with the space group P 6 bar c2 is energetically more stable than the P 6 bar m2 phase. We systematically investigated its electronic, optical, vibrational, infrared, and elastic properties. The results reveal that KCdCO3F is a direct-band-gap insulator with rather flat bands below the Fermi level. Analyses of its partial density of states revealed that the top (bottom) of its valence (conduction) band is formed by the O 2p (Cd 5s) orbital. It is a negative uniaxial crystal with ionic-covalent nature. Both infrared-active and Raman-active modes exist at its Brillouin zone center, and ions contribute more to its static dielectric constants. Its optical spectra in the visual and infrared ranges were studied, and their origins were revealed. Calculations indicate that KCdCO3F is mechanically stable but anisotropic since it is more vulnerable to shear stress and is easy to cleave along the c axis.

The lanthanum gallate-based mixed conducting perovskite ceramics

NASA Astrophysics Data System (ADS)

Politova, E. D.; Stefanovich, S. Yu.; Aleksandrovskii, V. V.; Kaleva, G. M.; Mosunov, A. V.; Avetisov, A. K.; Sung, J. S.; Choo, K. Y.; Kim, T. H.

2005-01-01

The structure, microstructure, dielectric, and transport properties of the anion deficient perovskite solid solutions (La,Sr)(Ga,Mg,M)O3- with M=Fe, Ni have been studied. Substitution of iron and nickel for gallium up to about 20 and 40 at.% respectively, leads to the perovskite lattice contraction due to the cation substitutions by the transition elements. The transition from pure ionic to mixed ionic-electronic conductivity was observed for both the systems studied. Both the enhancement of total conductivity and increasing in the thermal expansion coefficient values has been proved to correlate with the increasing amount of weakly bounded oxygen species in the Fe or Ni-doped ceramics. The oxygen ionic conductivity has been estimated from the kinetic experiments using the dc-conductivity and dilatometry methods under the condition of the stepwise change of the atmosphere from nitrogen to oxygen.

Molecular dynamics simulation of low dielectric constant polymer electrolytes

NASA Astrophysics Data System (ADS)

Wheatle, Bill; Lynd, Nathaniel; Ganesan, Venkat

Recent experimental studies measured the ionic conductivities of a series of poly(glycidyl ether)s with varying neat dielectric constants (ɛ), viscosities (η), and glass transition temperatures (Tg), as hosts for lithium bistrifluoromethanesulfonimide (LiTFSI) salt. In such a context, it was demonstrated that the ionic conductivity of these polymer electrolytes was a function of ɛ rather than Tg or η, suggesting that there may exist regimes in which ionic conductivity is not limited by slow segmental dynamics but rather by low ionic dissociation. Motivated by such results, we used atomistic molecular dynamics to study the structure and transport characteristics of the same set of host polymers. We found that the coordination number of TFSI- about Li+ in the first solvation shell and the total fraction of free ions increased as a function of ɛ, implying the polymer hosts enhanced ion dissociation. In addition, we found that increasing the dielectric constant of the host polymer enhanced self-correlated ion transport, as evidenced by an increase in the diffusion coefficients of each ion species. Overall, we confirmed that limited ion dissociation in low- ɛ polymer electrolyte hosts hampers ionic conductivity. We would like to thank the National Science Foundation Graduate Research Fellowship Program for funding this research endeavor.

Simultaneous improvement in ionic conductivity and flexibility of solid polymer electrolytes for thin film lithium ion batteries

NASA Astrophysics Data System (ADS)

Ji, Jianying

Solid polymer electrolytes (SPEs) provide advantages over liquid electrolytes in terms of safety, reliability, less temperature sensitive, and simplicity of design. With the use of a SPE in lithium batteries, high specific energy and specific power, safe operation, flexibility in packaging, and low cost of fabrication can be expected. However, after 30 years, SPEs have rarely found commercial success due to the low ionic conductivity and/or insufficient mechanical properties, both of which are related to the movement of the polymer chains. Many physical/chemical methods have been exploited to simultaneously create enhancement in ionic conductivity and mechanical properties, and some suggested ways have shown promise. However, the complex strategies have always introduced other challenge issues and incurred extra costs for manufacturing. In such a context, the development of dry solid state electrolytes is the central challenge to be faced worldwide. This thesis deals with the approaches to improving ionic conductivity and mechanical properties simultaneously. The method is to apply two kinds of controllable organic fillers: copolymer and protein. Our work revealed that the commercial available copolymer, poly (ethylene oxide)- block-polyethylene (PEO-b-PE), possesses a capability for enhancing the multiple performances of poly(ethylene oxide)(PEO)-based polymer electrolyte. And the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs were examined. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties, while increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity. A rubber-like, soy protein-based SPE (s-SPE)was obtained by employing soy protein isolate (SPI), a soy product usually used as rigid fillers for enhancing mechanical properties of polymers, blended with poly(ethylene oxide)(PEO). The results indicated that the s-SPE with 55 wt% of SPI possesses a fully amorphous uniform structure having low Tg, in contrast with crystalline PEO-based SPE having discernable Tg and Tm. The conductivity and elasticity are both significantly improved with SPI involvement. Remarkably, this film has been elongated up to 100% without loss of ionic conductivity and 700% without mechanical damage.

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

NASA Astrophysics Data System (ADS)

Acree, William; Chickos, James S.

2017-03-01

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids.

PubMed

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situ scanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situ STM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situ microscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).

Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air

PubMed Central

Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

2016-01-01

Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection. PMID:27070588

Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air.

PubMed

Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

2016-04-08

Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m²/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

Influence Of Zwitterions on Properties and Morphology of Ionomers: Implications for Electro-Active Applications

DTIC Science & Technology

2010-08-01

membranes in EMIm ES ionic liquid at 10 wt% IL concentration resulted in composites with similar mechanical performance, but 1. REPORT DATE (DD-MM...TERMS zwitterionomer, thermal mechanical property, morphology, ionic liquid , ionic conductivity, transducer Tianyu Wu, Rebecca H. Brown, Andrew J. Duncan...expected entanglement concentration. Swelling of the zwitterionomer membranes in EMIm ES ionic liquid at 10 wt% IL concentration resulted in

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

PubMed

Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

2016-02-10

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Anisotropic thermal conductive MWCNT/polymer composites prepared with an immiscible PS/LDPE blend.

PubMed

Kwon, Younghwan

2014-08-01

This study focuses on MWCNT/polymer composites with flexible, anisotropic heat transporting properties. For this study, an immiscible polymer blend of MWCNT/PS and LDPE (13.5:86.5 v:v) were used as a template. MWCNT/PS composites were first prepared by a solution process, and then melt-blended with LDPE using a brabender mixer. For achieving an alignment of MWCNT/PS in LDPE matrix, the blends of MWCNT/PS and LDPE were continuously treated under a fixed shear rate of 10 s(-1) at 210 °C. With partial extraction of PS in the aligned blends, FE-SEM images of the aligned blends revealed morphology of MWCNT in the PS/LDPE matrix, indicating local distribution of MWCNT selectively inside PS, where PS was elongated parallel to shear direction in LDPE matrix. The prepared MWCNT/PS and LDPE blends showed an anisotropic heat transporting behavior with anisotropic ratio of thermal conductivity (AR = λx/λz) up to 1.330 at 10 wt% of MWCNT in PS (equivalent to 1.50 wt% of MWCNT in PS/LDPE).

Novel anisotropic engineered cardiac tissues: studies of electrical propagation.

PubMed

Bursac, Nenad; Loo, Yihua; Leong, Kam; Tung, Leslie

2007-10-05

The goal of this study was to engineer cardiac tissue constructs with uniformly anisotropic architecture, and to evaluate their electrical function using multi-site optical mapping of cell membrane potentials. Anisotropic polymer scaffolds made by leaching of aligned sucrose templates were seeded with neonatal rat cardiac cells and cultured in rotating bioreactors for 6-14 days. Cells aligned and interconnected inside the scaffolds and when stimulated by a point electrode, supported macroscopically continuous, anisotropic impulse propagation. By culture day 14, the ratio of conduction velocities along vs. across cardiac fibers reached a value of 2, similar to that in native neonatal ventricles, while action potential duration and maximum capture rate, respectively, decreased to 120ms and increased to approximately 5Hz. The shorter culture time and larger scaffold thickness were associated with increased incidence of sustained reentrant arrhythmias. In summary, this study is the first successful attempt to engineer a cm(2)-size, functional anisotropic cardiac tissue patch.

Acidic Ionic Liquids.

PubMed

Amarasekara, Ananda S

2016-05-25

Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition.

A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

DOE PAGES

Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; ...

2016-10-31

Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na + ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm –1 at 25°C and 14 ms cmmore » –1 at 80°C.« less

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

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

PubMed

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

2011-01-21

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

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

PubMed Central

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

2011-01-01

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

Characterization of chitosan-starch blend based biopolymer electrolyte doped with ammonium nitrate

NASA Astrophysics Data System (ADS)

Shaffie, Ahmad Hakimi; Khiar, Azwani Sofia Ahmad

2018-06-01

Polymer electrolyte is an ionic conductor formed by dissolving salt in polymer host. In this work, starch/chitosan blend based polymer electrolyte was prepared with different weight percentage of Ammonium Nitrate (NH4NO3) via solution casting technique. The film was characterized by impedance spectroscopy HIOKI 3531- 01 LCR Hi-Tester to measure its ionic conductivity over a wide range of frequency between 50Hz-5MHz and at ambient temperature. Sample with 35 wt% of NH4NO3 shows the highest conductivity of (6.34 ± 1.52) = 10-7 Scm-1. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to correlate the ionic conductivity results.

Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

DOEpatents

Van Calcar, Pamela; Mackay, Richard; Sammells, Anthony F.

2002-01-01

The invention relates to mixed phase materials for the preparation of catalytic membranes which exhibit ionic and electronic conduction and which exhibit improved mechanical strength compared to single phase ionic and electronic conducting materials. The mixed phase materials are useful for forming gas impermeable membranes either as dense ceramic membranes or as dense thin films coated onto porous substrates. The membranes and materials of this invention are useful in catalytic membrane reactors in a variety of applications including synthesis gas production. One or more crystalline second phases are present in the mixed phase material at a level sufficient to enhance the mechanical strength of the mixture to provide membranes for practical application in CMRs.

Cellulose ionics: switching ionic diode responses by surface charge in reconstituted cellulose films.

PubMed

Aaronson, Barak D B; Wigmore, David; Johns, Marcus A; Scott, Janet L; Polikarpov, Igor; Marken, Frank

2017-09-25

Cellulose films as well as chitosan-modified cellulose films of approximately 5 μm thickness, reconstituted from ionic liquid media onto a poly(ethylene-terephthalate) (PET, 6 μm thickness) film with a 5, 10, 20, or 40 μm diameter laser-drilled microhole, show significant current rectification in aqueous NaCl. Reconstituted α-cellulose films provide "cationic diodes" (due to predominant cation conductivity) whereas chitosan-doped cellulose shows "anionic diode" effects (due to predominant anion conductivity). The current rectification, or "ionic diode" behaviour, is investigated as a function of NaCl concentration, pH, microhole diameter, and molecular weight of the chitosan dopant. Future applications are envisaged exploiting the surface charge induced switching of diode currents for signal amplification in sensing.

Evaluation of the Anisotropic Radiative Conductivity of a Low-Density Carbon Fiber Material from Realistic Microscale Imaging

NASA Technical Reports Server (NTRS)

Nouri, Nima; Panerai, Francesco; Tagavi, Kaveh A.; Mansour, Nagi N.; Martin, Alexandre

2015-01-01

The radiative heat transfer inside a low-density carbon fiber insulator is analyzed using a three-dimensional direct simulation model. A robust procedure is presented for the numerical calculation of the geometric configuration factor to compute the radiative energy exchange processes among the small discretized surface areas of the fibrous material. The methodology is applied to a polygonal mesh of a fibrous insulator obtained from three-dimensional microscale imaging of the real material. The anisotropic values of the radiative conductivity are calculated for that geometry. The results yield both directional and thermal dependence of the radiative conductivity.

Direct mapping of ion diffusion times on LiCoO2 surfaces with nanometer resolution

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

Guo, Senli; Jesse, Stephen; Kalnaus, Sergiy

2011-01-01

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

Application of Ionic Liquids in Hydrometallurgy

PubMed Central

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

2014-01-01

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

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2].

PubMed

Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter; Jacquemin, Johan; Pionteck, Jürgen; Hensel-Bielowka, Stella

2015-08-28

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Flake-like oxygen-deficient lithium vanadium oxides as a high ionic and electronic conductive cathode material for high-power Li-ion battery

NASA Astrophysics Data System (ADS)

Li, Jing-quan; Han, Chong; Jing, Mao-xiang; Yang, Hua; Shen, Xiang-qian; Qin, Shi-biao

2018-06-01

Low electronic and ionic conductivity for LiV3O8 cathode material could lead to poor cycling stability and rate capability, which are considered as the main restraint for its application in Li-ion battery. A novel flake-like LiV3O7.9 material modified by high ionic and electronic conductive Li0.3V2O5/C was fabricated via electrospinning and controlled thermal sintering processes. This oxygen-deficient LiV3O7.9/Li0.3V2O5-C composite electrode sintered at 500 °C exhibits improved rate and cycle stability. The electrode possesses a retention capacity of 151.9mAh/g after 500 cycles at 5C and 84.8mAh/g after 1000 cycles at 10C, respectively. The improvement of the electrochemical performance could be attributed to the synergistic effects of flake-like morphology, oxygen-deficiency and surface modification of Li0.3V2O5/C, which increase the ionic and electronic conductivity of LiV3O8.

Strain tuning and strong enhancement of ionic conductivity in SrZrO 3-RE 2O 3 (RE = Sm, Eu, Gd, Dy, and Er) nanocomposite films

DOE PAGES

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; ...

2015-06-05

Fast ion transport channels at interfaces in thin films have attracted great attention due to a range of potential applications for energy materials and devices, for, solid oxide fuel cells, sensors, and memories. Here, it is shown that in vertical nanocomposite heteroepitaxial films of SrZrO 3–RE 2O 3 (RE = Sm, Eu, Gd, Dy, and Er) the ionic conductivity of the composite can be tuned and strongly enhanced using embedded, stiff, and vertical nanopillars of RE 2O 3. With increasing lattice constant of RE 2O 3 from Er 2O 3 to Sm 2O 3, it is found that the tensilemore » strain in the SrZrO 3 increases proportionately, and the ionic conductivity of the composite increases accordingly, by an order of magnitude. Lastly, the results here conclusively show, for the first time, that strain in films can be effectively used to tune the ionic conductivity of the materials.« less

Aggregate-mediated charge transport in ionomeric electrolytes

NASA Astrophysics Data System (ADS)

Lu, Keran; Maranas, Janna; Milner, Scott

Polymers such PEO can conduct ions, and have been studied as possible replacements for organic liquid electrolytes in rechargeable metal-ion batteries. More generally, fast room-temperature ionic conduction has been reported for a variety of materials, from liquids to crystalline solids. Unfortunately, polymer electrolytes generally have limited conductivity; these polymers are too viscous to have fast ion diffusion like liquids, and too unstructured to promote cooperative transport like crystalline solids. Ionomers are polymer electrolytes in which ionic groups are covalently bound to the polymer backbone, neutralized by free counterions. These materials also conduct ions, and can exhibit strong ionic aggregation. Using coarse-grained molecular dynamics, we explore the forces driving ionic aggregation, and describe the role ion aggregates have in mediating charge transport. The aggregates are string-like such that ions typically have two neighbors. We find ion aggregates self-assemble like worm-like micelles. Excess charge, or free ions, occasionally coordinate with aggregates and are transported along the chain in a Grotthuss-like mechanism. We propose that controlling ionomer aggregate structure through materials design can enhance cooperative ion transport.

Aerospace Power Scholarly Research Program. Delivery Order 0011: Modeling Lithium-Ion Conducting Channel

DTIC Science & Technology

2005-12-01

Brinkmann, D. NMR, DSC, and conductivity study of a poly (ethylene oxide) complex electrolyte: PEO(LiClO4)x, Sol. St. Ionics 1986, 18-19, 295. (27...Electrochemical Characterizations of Dilithium Octacyanophthalocyanine Langmuir - Blodgett films, Langmuir 2002, 18, 2223. 20 ...phthalocyanine (Li2Pc) has been used in this development since it can undergo molecular self-assembly to form the ionic ally conducting channel. The

The Effect of Structural Modifications on Ionic Conductivity in Newly-Designed Polyester Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Jung, Yuki; Coates, Geoff; Balsara, Nitash

2015-03-01

Gaining a fundamental understanding of the relationship between molecular structure and ionic conductivity of polymer electrolytes is an essential step toward designing next generation materials for battery applications. In this study, we use a systematic set of newly-designed polyesters with varying side-chain lengths and oxygen functional groups to elucidate the effects of structural modifications on the conductive properties of the corresponding electrolytes. Mixtures of polyesters and lithium bis(trifluromethanesulfonyl)imide (LiTFSI) were characterized using ac impedance spectroscopy to measure the ionic conductivity at various temperatures and salt concentrations. The relative conductivities of these electrolytes in the dilute limit are directly comparable to results of molecular dynamics simulations performed using the same polymers. The simulations correspond well with the experimental results, and provide molecular level insight about the solvation environment of the lithium ions and how the ions transport through these polyesters.

Effects of anisotropic conduction and heat pipe interaction on minimum mass space radiators

NASA Technical Reports Server (NTRS)

Baker, Karl W.; Lund, Kurt O.

1991-01-01

Equations are formulated for the two dimensional, anisotropic conduction of heat in space radiator fins. The transverse temperature field was obtained by the integral method, and the axial field by numerical integration. A shape factor, defined for the axial boundary condition, simplifies the analysis and renders the results applicable to general heat pipe/conduction fin interface designs. The thermal results are summarized in terms of the fin efficiency, a radiation/axial conductance number, and a transverse conductance surface Biot number. These relations, together with those for mass distribution between fins and heat pipes, were used in predicting the minimum radiator mass for fixed thermal properties and fin efficiency. This mass is found to decrease monotonically with increasing fin conductivity. Sensitivities of the minimum mass designs to the problem parameters are determined.

Ionomer Design, Synthesis and Characterization for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph H.

2013-03-01

For ionic actuators and battery separators, it is vital to utilize single-ion conductors that avoid the detrimental polarization of other ions; the commonly studied dual-ion conductors simply will not be used in the next generation of materials for these applications. Ab initio quantum chemistry calculations at 0 K in vacuum characterize ion interactions and ion solvation by various functional groups, allowing identification of constituents with weak interactions to be incorporated in ionomers for facile ion transport. Simple ideas for estimating the ion interactions and solvation at practical temperatures and dielectric constants are presented that indicate the rank ordering observed at 0 K in vacuum should be preserved. Hence, such ab initio calculations are useful for screening the plethora of combinations of polymer-ion, counterion and polar functional groups, to decide which are worthy of synthesis for new ionomers. Single-ion conducting ionomers are synthesized based on these calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for ionic actuators and battery separators. Characterization by X-ray scattering, dielectric spectroscopy, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. Examples are shown of how ab initio calculations can be used to understand experimental observations of dielectric constant, glass transition temperature and conductivity of polymerized ionic liquids with counterions being either lithium, sodium, fluoride, hydroxide (for batteries) or bulky ionic liquids (for ionic actuators). This work was supported by the Department of Energy under Grant BES-DE-FG02-07ER46409.

Importance of liquid fragility for energy applications of ionic liquids

NASA Astrophysics Data System (ADS)

Sippel, Pit; Lunkenheimer, Peter; Krohns, Stephan; Thoms, Erik; Loidl, Alois

Ionic liquids (ILs) are salts that are liquid at ambient temperatures. The strong electrostatic forces between their molecular ions result, e.g., in low volatility and high stability for many members of this huge material class. For this reason they bear a high potential for new advancements in applications, e.g., as electrolytes in energy-storage devices such as supercapacitors or batteries, where the ionic conductivity is an essential figure of merit. Most ILs show dynamic properties typical for glassy matter, which dominate many of their physical properties. An important method to study these dynamical glass-properties is dielectric spectroscopy that can access relaxation times of dynamic processes and the conductivity in a broad frequency and temperature range. In the present contribution, we present results on a large variety of ionic liquids showing that the conductivity of ILs depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility. This work was supported by the Deutsche Forschungsgemeinschaft via Research Unit FOR1394 and by the BMBF via ENREKON 03EK3015.

Anisotropic diffusion in mesh-free numerical magnetohydrodynamics

NASA Astrophysics Data System (ADS)

Hopkins, Philip F.

2017-04-01

We extend recently developed mesh-free Lagrangian methods for numerical magnetohydrodynamics (MHD) to arbitrary anisotropic diffusion equations, including: passive scalar diffusion, Spitzer-Braginskii conduction and viscosity, cosmic ray diffusion/streaming, anisotropic radiation transport, non-ideal MHD (Ohmic resistivity, ambipolar diffusion, the Hall effect) and turbulent 'eddy diffusion'. We study these as implemented in the code GIZMO for both new meshless finite-volume Godunov schemes (MFM/MFV). We show that the MFM/MFV methods are accurate and stable even with noisy fields and irregular particle arrangements, and recover the correct behaviour even in arbitrarily anisotropic cases. They are competitive with state-of-the-art AMR/moving-mesh methods, and can correctly treat anisotropic diffusion-driven instabilities (e.g. the MTI and HBI, Hall MRI). We also develop a new scheme for stabilizing anisotropic tensor-valued fluxes with high-order gradient estimators and non-linear flux limiters, which is trivially generalized to AMR/moving-mesh codes. We also present applications of some of these improvements for SPH, in the form of a new integral-Godunov SPH formulation that adopts a moving-least squares gradient estimator and introduces a flux-limited Riemann problem between particles.

Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

PubMed

Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

2012-04-07

Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

Ionic Conductivity Increased by Two Orders of Magnitude in Micrometer-Thick Vertical Yttria-Stabilized ZrO 2 Nanocomposite Films

DOE PAGES

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; ...

2015-09-03

We design and create a unique cell geometry of templated micrometer-thick epitaxial nanocomposite films which contain ~20 nm diameter yttria-stabilized ZrO 2 (YSZ) nanocolumns, strain coupled to a SrTiO 3 matrix. We also enhanced the ionic conductivity of these nanocolumnsby over 2 orders of magnitude compared to plain YSZ films. Concomitant with the higher ionic conduction is the finding that the YSZ nanocolumns in the films have much higher crystallinity and orientation, compared to plain YSZ films. Hence, “oxygen migration highways” are formed in the desired out-of-plane direction. This improved structure is shown to originate from the epitaxial coupling ofmore » the YSZ nanocolumns to the SrTiO 3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO 2 nanocolumns within the SrTiO 3 matrix. Furthermore, this intermediate layer reduces the lattice mismatch between the YSZ nanocolumns and the substrate. Vertical ionic conduction values as high as 10 –2 Ω –1 cm –1 were demonstrated at 360 °C (300 °C lower than plain YSZ films), showing the strong practical potential of these nanostructured films for use in much lower operation temperature ionic devices.« less

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

PubMed

Yan, Yunsong; Santaniello, Tommaso; Bettini, Luca Giacomo; Minnai, Chloé; Bellacicca, Andrea; Porotti, Riccardo; Denti, Ilaria; Faraone, Gabriele; Merlini, Marco; Lenardi, Cristina; Milani, Paolo

2017-06-01

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm -2 ), high electrochemical capacitance (≈mF g -1 ), and minimal mechanical stress at the polymer/metal composite interface upon deformation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

DOE PAGES

Fan, Fei; Wang, Weiyu; Holt, Adam P.; ...

2016-06-07

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

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

Fan, Fei; Wang, Weiyu; Holt, Adam P.

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Combined flame and electrodeposition synthesis of energetic coaxial tungsten-oxide/aluminum nanowire arrays.

PubMed

Dong, Zhizhong; Al-Sharab, Jafar F; Kear, Bernard H; Tse, Stephen D

2013-09-11

A nanostructured thermite composite comprising an array of tungsten-oxide (WO2.9) nanowires (diameters of 20-50 nm and lengths of >10 μm) coated with single-crystal aluminum (thickness of ~16 nm) has been fabricated. The method involves combined flame synthesis of tungsten-oxide nanowires and ionic-liquid electrodeposition of aluminum. The geometry not only presents an avenue to tailor heat-release characteristics due to anisotropic arrangement of fuel and oxidizer but also eliminates or minimizes the presence of an interfacial Al2O3 passivation layer. Upon ignition, the energetic nanocomposite exhibits strong exothermicity, thereby being useful for fundamental study of aluminothermic reactions as well as enhancing combustion characteristics.

Mechanical, Thermodynamic and Electronic Properties of Wurtzite and Zinc-Blende GaN Crystals.

PubMed

Qin, Hongbo; Luan, Xinghe; Feng, Chuang; Yang, Daoguo; Zhang, Guoqi

2017-12-12

For the limitation of experimental methods in crystal characterization, in this study, the mechanical, thermodynamic and electronic properties of wurtzite and zinc-blende GaN crystals were investigated by first-principles calculations based on density functional theory. Firstly, bulk moduli, shear moduli, elastic moduli and Poisson's ratios of the two GaN polycrystals were calculated using Voigt and Hill approximations, and the results show wurtzite GaN has larger shear and elastic moduli and exhibits more obvious brittleness. Moreover, both wurtzite and zinc-blende GaN monocrystals present obvious mechanical anisotropic behavior. For wurtzite GaN monocrystal, the maximum and minimum elastic moduli are located at orientations [001] and <111>, respectively, while they are in the orientations <111> and <100> for zinc-blende GaN monocrystal, respectively. Compared to the elastic modulus, the shear moduli of the two GaN monocrystals have completely opposite direction dependences. However, different from elastic and shear moduli, the bulk moduli of the two monocrystals are nearly isotropic, especially for the zinc-blende GaN. Besides, in the wurtzite GaN, Poisson's ratios at the planes containing [001] axis are anisotropic, and the maximum value is 0.31 which is located at the directions vertical to [001] axis. For zinc-blende GaN, Poisson's ratios at planes (100) and (111) are isotropic, while the Poisson's ratio at plane (110) exhibits dramatically anisotropic phenomenon. Additionally, the calculated Debye temperatures of wurtzite and zinc-blende GaN are 641.8 and 620.2 K, respectively. At 300 K, the calculated heat capacities of wurtzite and zinc-blende are 33.6 and 33.5 J mol -1 K -1 , respectively. Finally, the band gap is located at the G point for the two crystals, and the band gaps of wurtzite and zinc-blende GaN are 3.62 eV and 3.06 eV, respectively. At the G point, the lowest energy of conduction band in the wurtzite GaN is larger, resulting in a wider band gap. Densities of states in the orbital hybridization between Ga and N atoms of wurtzite GaN are much higher, indicating more electrons participate in forming Ga-N ionic bonds in the wurtzite GaN.

Mechanical, Thermodynamic and Electronic Properties of Wurtzite and Zinc-Blende GaN Crystals

PubMed Central

Luan, Xinghe; Feng, Chuang; Yang, Daoguo; Zhang, Guoqi

2017-01-01

For the limitation of experimental methods in crystal characterization, in this study, the mechanical, thermodynamic and electronic properties of wurtzite and zinc-blende GaN crystals were investigated by first-principles calculations based on density functional theory. Firstly, bulk moduli, shear moduli, elastic moduli and Poisson’s ratios of the two GaN polycrystals were calculated using Voigt and Hill approximations, and the results show wurtzite GaN has larger shear and elastic moduli and exhibits more obvious brittleness. Moreover, both wurtzite and zinc-blende GaN monocrystals present obvious mechanical anisotropic behavior. For wurtzite GaN monocrystal, the maximum and minimum elastic moduli are located at orientations [001] and <111>, respectively, while they are in the orientations <111> and <100> for zinc-blende GaN monocrystal, respectively. Compared to the elastic modulus, the shear moduli of the two GaN monocrystals have completely opposite direction dependences. However, different from elastic and shear moduli, the bulk moduli of the two monocrystals are nearly isotropic, especially for the zinc-blende GaN. Besides, in the wurtzite GaN, Poisson’s ratios at the planes containing [001] axis are anisotropic, and the maximum value is 0.31 which is located at the directions vertical to [001] axis. For zinc-blende GaN, Poisson’s ratios at planes (100) and (111) are isotropic, while the Poisson’s ratio at plane (110) exhibits dramatically anisotropic phenomenon. Additionally, the calculated Debye temperatures of wurtzite and zinc-blende GaN are 641.8 and 620.2 K, respectively. At 300 K, the calculated heat capacities of wurtzite and zinc-blende are 33.6 and 33.5 J mol−1 K−1, respectively. Finally, the band gap is located at the G point for the two crystals, and the band gaps of wurtzite and zinc-blende GaN are 3.62 eV and 3.06 eV, respectively. At the G point, the lowest energy of conduction band in the wurtzite GaN is larger, resulting in a wider band gap. Densities of states in the orbital hybridization between Ga and N atoms of wurtzite GaN are much higher, indicating more electrons participate in forming Ga-N ionic bonds in the wurtzite GaN. PMID:29231902

Research@ARL: Materials Modeling at Multiple Scales. Volume 3, Issue 2

DTIC Science & Technology

2014-07-01

possessing high ionic conductivity , low viscosity, and good thermal and electrochemical stability and, importantly, being compatible with electrodes. As... thermal and electrical properties. ARL conducts extensive research in graphene and other 2D materials such as BN, ZnO, and hybrid graphene-polyethylene...contribution at temperatures below 393 K. Thus, below 393 K, Li2EDC essentially acts as a single ion conductor . The isotropic ionic conductivity from MD

Non-Arrhenius ionic conductivities in glasses due to a distribution of activation energies.

PubMed

Bischoff, C; Schuller, K; Beckman, S P; Martin, S W

2012-08-17

Previously observed non-Arrhenius behavior in fast ion conducting glasses [J. Kincs and S. W. Martin, Phys. Rev. Lett. 76, 70 (1996)] occurs at temperatures near the glass transition temperature, T(g), and is attributed to changes in the ion mobility due to ion trapping mechanisms that diminish the conductivity and result in a decreasing conductivity with increasing temperature. It is intuitive that disorder in glass will also result in a distribution of the activation energies (DAE) for ion conduction, which should increase the conductivity with increasing temperature, yet this has not been identified in the literature. In this Letter, a series of high precision ionic conductivity measurements are reported for 0.5Na(2)S + 0.5[xGeS(2) + (1-x)PS(5/2)] glasses with compositions ranging from 0 ≤ x ≤ 1. The impact of the cation site disorder on the activation energy is identified and explained using a DAE model. The absence of the non-Arrhenius behavior in other glasses is explained and it is predicted which glasses are expected to accentuate the DAE effect on the ionic conductivity.

Evolution of Anisotropic Displacement Parameters and Superconductivity with Chemical Pressure in BiS2-Based REO0.5F0.5BiS2 (RE = La, Ce, Pr, and Nd)

NASA Astrophysics Data System (ADS)

Mizuguchi, Yoshikazu; Hoshi, Kazuhisa; Goto, Yosuke; Miura, Akira; Tadanaga, Kiyoharu; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2018-02-01

In order to understand the mechanisms behind the emergence of superconductivity by the chemical pressure effect in REO0.5F0.5BiS2 (RE = La, Ce, Pr, and Nd), where bulk superconductivity is induced by the substitutions with a smaller-radius RE, we performed synchrotron powder X-ray diffraction, and analyzed the crystal structure and anisotropic displacement parameters. With the decrease of the RE3+ ionic radius, the in-plane disorder of the S1 sites significantly decreased, very similar to the trend observed in the Se-substituted systems: LaO0.5F0.5BiS2-xSex and Eu0.5La0.5FBiS2-xSex. Therefore, the emergence of bulk superconductivity upon the suppression of the in-plane disorder at the chalcogen sites is a universal scenario for the BiCh2-based superconductors. In addition, we indicated that the amplitude of vibration along the c-axis of the in-plane chalcogen sites may be related to the Tc in the BiCh2-based superconductors.

The Effect of Ionic Strength on the Solubility of an Electrolyte

ERIC Educational Resources Information Center

Willey, Joan D.

2004-01-01

A simple experiment was conducted for studying and demonstrating visually and dramatically the effect of ionic strength on the solubility of an electrolyte is described. It is seen that the experiment visually illustrates the effect of ionic strength on electrolyte solubility by the appearance of the two solutions and by the difference in the…

Thermal boundary conductance of hydrophilic and hydrophobic ionic liquids

NASA Astrophysics Data System (ADS)

Oyake, Takafumi; Sakata, Masanori; Yada, Susumu; Shiomi, Junichiro

2015-03-01

A solid/liquid interface plays a critical role for understanding mechanisms of biological and physical science. Moreover, carrier density of the surface is dramatically enhanced by electric double layer with ionic liquid, salt in the liquid state. Here, we have measured the thermal boundary conductance (TBC) across an interface of gold thin film and ionic liquid by using time-domain thermoreflectance technique. Following the prior researches, we have identified the TBC of two interfaces. One is gold and hydrophilic ionic liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF4), which is a hydrophilic ionic liquid, and the other is N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI), which is a hydrophobic ionic liquid. We found that the TBC between gold and DEME-TFIS (19 MWm-2K-1) is surprisingly lower than the interface between gold and DEME-BF4 (45 MWm-2K-1). With these data, the importance of the wetting angle and ion concentration for the thermal transport at the solid/ionic liquid interface is discussed. Part of this work is financially supported by Japan Society for the Promotion of Science (JSPS) and Japan Science and Technology Agency. The author is financially supported by JSPS Fellowship.

Anisotropic thermal conductivity in epoxy-bonded magnetocaloric composites

NASA Astrophysics Data System (ADS)

Weise, Bruno; Sellschopp, Kai; Bierdel, Marius; Funk, Alexander; Bobeth, Manfred; Krautz, Maria; Waske, Anja

2016-09-01

Thermal management is one of the crucial issues in the development of magnetocaloric refrigeration technology for application. In order to ensure optimal exploitation of the materials "primary" properties, such as entropy change and temperature lift, thermal properties (and other "secondary" properties) play an important role. In magnetocaloric composites, which show an increased cycling stability in comparison to their bulk counterparts, thermal properties are strongly determined by the geometric arrangement of the corresponding components. In the first part of this paper, the inner structure of a polymer-bonded La(Fe, Co, Si)13-composite was studied by X-ray computed tomography. Based on this 3D data, a numerical study along all three spatial directions revealed anisotropic thermal conductivity of the composite: Due to the preparation process, the long-axis of the magnetocaloric particles is aligned along the xy plane which is why the in-plane thermal conductivity is larger than the thermal conductivity along the z-axis. Further, the study is expanded to a second aspect devoted to the influence of particle distribution and alignment within the polymer matrix. Based on an equivalent ellipsoids model to describe the inner structure of the composite, numerical simulation of the thermal conductivity in different particle arrangements and orientation distributions were performed. This paper evaluates the possibilities of microstructural design for inducing and adjusting anisotropic thermal conductivity in magnetocaloric composites.

Influence of topological transitions in a quantizing magnetic field and anisotropy of current carrier scattering by acoustic phonons on the longitudinal electrical conductivity of layered crystals with open fermi surfaces

NASA Astrophysics Data System (ADS)

Gorskii, P. V.

2011-03-01

It is demonstrated that the dependence of Fermi's energy on the magnetic field causes a set of the Shubnikov - de Haas (SDH) oscillation frequencies to change, and their relative contribution to the total longitudinal conductivity of layered crystals depends on whether the scattering of current carriers is isotropic or anisotropic. Owing to the topological transition in a strong magnetic field, Fermi's surface (FS) is transformed from open into closed one and is compressed in the magnetic field direction. Therefore, in an ultraquantum limit, disregarding the Dingle factor, the longitudinal electrical conductivity of the layered crystal tends to zero as a reciprocal square of the magnetic field for the isotropic scattering and as a reciprocal cube of the magnetic field for the anisotropic scattering. All calculations are performed in the approximation of relaxation time considered to be constant versus the quantum numbers for the isotropic scattering and proportional to the longitudinal velocity of current carriers for the anisotropic scattering.

Hybrid hydrogels containing vertically aligned carbon nanotubes with anisotropic electrical conductivity for muscle myofiber fabrication.

PubMed

Ahadian, Samad; Ramón-Azcón, Javier; Estili, Mehdi; Liang, Xiaobin; Ostrovidov, Serge; Shiku, Hitoshi; Ramalingam, Murugan; Nakajima, Ken; Sakka, Yoshio; Bae, Hojae; Matsue, Tomokazu; Khademhosseini, Ali

2014-03-19

Biological scaffolds with tunable electrical and mechanical properties are of great interest in many different fields, such as regenerative medicine, biorobotics, and biosensing. In this study, dielectrophoresis (DEP) was used to vertically align carbon nanotubes (CNTs) within methacrylated gelatin (GelMA) hydrogels in a robust, simple, and rapid manner. GelMA-aligned CNT hydrogels showed anisotropic electrical conductivity and superior mechanical properties compared with pristine GelMA hydrogels and GelMA hydrogels containing randomly distributed CNTs. Skeletal muscle cells grown on vertically aligned CNTs in GelMA hydrogels yielded a higher number of functional myofibers than cells that were cultured on hydrogels with randomly distributed CNTs and horizontally aligned CNTs, as confirmed by the expression of myogenic genes and proteins. In addition, the myogenic gene and protein expression increased more profoundly after applying electrical stimulation along the direction of the aligned CNTs due to the anisotropic conductivity of the hybrid GelMA-vertically aligned CNT hydrogels. We believe that platform could attract great attention in other biomedical applications, such as biosensing, bioelectronics, and creating functional biomedical devices.

Hybrid hydrogels containing vertically aligned carbon nanotubes with anisotropic electrical conductivity for muscle myofiber fabrication

PubMed Central

Ahadian, Samad; Ramón-Azcón, Javier; Estili, Mehdi; Liang, Xiaobin; Ostrovidov, Serge; Shiku, Hitoshi; Ramalingam, Murugan; Nakajima, Ken; Sakka, Yoshio; Bae, Hojae; Matsue, Tomokazu; Khademhosseini, Ali

2014-01-01

Biological scaffolds with tunable electrical and mechanical properties are of great interest in many different fields, such as regenerative medicine, biorobotics, and biosensing. In this study, dielectrophoresis (DEP) was used to vertically align carbon nanotubes (CNTs) within methacrylated gelatin (GelMA) hydrogels in a robust, simple, and rapid manner. GelMA-aligned CNT hydrogels showed anisotropic electrical conductivity and superior mechanical properties compared with pristine GelMA hydrogels and GelMA hydrogels containing randomly distributed CNTs. Skeletal muscle cells grown on vertically aligned CNTs in GelMA hydrogels yielded a higher number of functional myofibers than cells that were cultured on hydrogels with randomly distributed CNTs and horizontally aligned CNTs, as confirmed by the expression of myogenic genes and proteins. In addition, the myogenic gene and protein expression increased more profoundly after applying electrical stimulation along the direction of the aligned CNTs due to the anisotropic conductivity of the hybrid GelMA-vertically aligned CNT hydrogels. We believe that platform could attract great attention in other biomedical applications, such as biosensing, bioelectronics, and creating functional biomedical devices. PMID:24642903

Hybrid hydrogels containing vertically aligned carbon nanotubes with anisotropic electrical conductivity for muscle myofiber fabrication

NASA Astrophysics Data System (ADS)

Ahadian, Samad; Ramón-Azcón, Javier; Estili, Mehdi; Liang, Xiaobin; Ostrovidov, Serge; Shiku, Hitoshi; Ramalingam, Murugan; Nakajima, Ken; Sakka, Yoshio; Bae, Hojae; Matsue, Tomokazu; Khademhosseini, Ali

2014-03-01

Biological scaffolds with tunable electrical and mechanical properties are of great interest in many different fields, such as regenerative medicine, biorobotics, and biosensing. In this study, dielectrophoresis (DEP) was used to vertically align carbon nanotubes (CNTs) within methacrylated gelatin (GelMA) hydrogels in a robust, simple, and rapid manner. GelMA-aligned CNT hydrogels showed anisotropic electrical conductivity and superior mechanical properties compared with pristine GelMA hydrogels and GelMA hydrogels containing randomly distributed CNTs. Skeletal muscle cells grown on vertically aligned CNTs in GelMA hydrogels yielded a higher number of functional myofibers than cells that were cultured on hydrogels with randomly distributed CNTs and horizontally aligned CNTs, as confirmed by the expression of myogenic genes and proteins. In addition, the myogenic gene and protein expression increased more profoundly after applying electrical stimulation along the direction of the aligned CNTs due to the anisotropic conductivity of the hybrid GelMA-vertically aligned CNT hydrogels. We believe that platform could attract great attention in other biomedical applications, such as biosensing, bioelectronics, and creating functional biomedical devices.

Adaptive finite element modelling of three-dimensional magnetotelluric fields in general anisotropic media

NASA Astrophysics Data System (ADS)

Liu, Ying; Xu, Zhenhuan; Li, Yuguo

2018-04-01

We present a goal-oriented adaptive finite element (FE) modelling algorithm for 3-D magnetotelluric fields in generally anisotropic conductivity media. The model consists of a background layered structure, containing anisotropic blocks. Each block and layer might be anisotropic by assigning to them 3 × 3 conductivity tensors. The second-order partial differential equations are solved using the adaptive finite element method (FEM). The computational domain is subdivided into unstructured tetrahedral elements, which allow for complex geometries including bathymetry and dipping interfaces. The grid refinement process is guided by a global posteriori error estimator and is performed iteratively. The system of linear FE equations for electric field E is solved with a direct solver MUMPS. Then the magnetic field H can be found, in which the required derivatives are computed numerically using cubic spline interpolation. The 3-D FE algorithm has been validated by comparisons with both the 3-D finite-difference solution and 2-D FE results. Two model types are used to demonstrate the effects of anisotropy upon 3-D magnetotelluric responses: horizontal and dipping anisotropy. Finally, a 3D sea hill model is modelled to study the effect of oblique interfaces and the dipping anisotropy.

Voltammetry and conductivity of a polyether-pyridinium room temperature molten salt electrolyte and of its polymer electrolyte solutions in polydimethylsiloxane

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

Pyati, R.; Murray, R.W.

1996-02-01

This report describes the synthesis, microelectrode voltammetry, and ionic conductivity of a new room temperature molten salt N-(methoxy(ethoxy){sub 2}ethyl)pyridinium p-toluene sulfonate (abbreviated as[Py(E{sub 3}M){sup +}][Tos{sup {minus}}]) and of its solution in a hydroxy-terminated polydimethylsiloxane. Both ionically conductive liquids (conductivity = 1 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1}) exhibit voltammetric potential windows of about 1.5 V. The negative potential limit is determined by the reduction of the [Py(E{sub 3}M){sup +}] pyridinium species, with subsequent radical coupling to form a voltammetrically observed viologen dimer. The estimated diffusivities of the [Py(E{sub 3}M){sup +}] species, of a diethyleneglycol-tailed ferrocene redox solute studied, andmore » by application of Nernst-Einstein relation to the ionic charge carriers, all lie in the 10{sup {minus}7} to 10{sup {minus}8} cm{sup 2}/s range. Viscosities and glass transition thermal observations are reported as is the fit of the temperature dependencies of ionic conductivity in [Py(E{sub 3}M){sup +}][Tos{sup {minus}}] and in [Py(E{sub 3}M){sup +}][TOS{sup {minus}}]/PDMS mixtures to Vogel-Tamman-Fulcher predictions.« less

Extremely dense microstructure and enhanced ionic conductivity in hot-isostatic pressing treated cubic garnet-type solid electrolyte of Ga2O3-doped Li7La3Zr2O12

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming’En; Hu, Zhiwei; Zhu, Jiliang

A large number of pores and a low relative density that are frequently observed in solid electrolytes reduce severely their ionic conductivity and thus limit their applicability. Here, we report on the use of hot isostatic pressing (HIP) for ameliorating the garnet-type lithium-ion conducting solid electrolyte of Ga2O3-doped Li7La3Zr2O12 (Ga-LLZO) with nominal composition of Li6.55Ga0.15La3Zr2O12. The Ga-LLZO pellets were conventionally sintered at 1075∘C for 12h, and then were followed by HIP treatment at 120MPa and 1160∘C under an Ar atmosphere. It is found that the HIP-treated Ga-LLZO shows an extremely dense microstructure and a significantly enhanced ionic conductivity. Coherent with the increase in relative density from 90.5% (untreated) to 97.5% (HIP-treated), the ionic conductivity of the HIP-treated Ga-LLZO reaches as high as 1.13×10‑3S/cm at room temperature (25∘C), being two times higher than that of 4.58×10‑4S/cm for the untreated one.

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

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

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

On the origin of high ionic conductivity in Na-doped SrSiO 3

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

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications.

PubMed

Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert

2009-06-01

A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

On the origin of high ionic conductivity in Na-doped SrSiO 3

DOE PAGES

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen; ...

2016-02-17

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

Carbon/PTFE Electrode for Lithium/Air-Water Batteries

DTIC Science & Technology

2007-03-01

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

Influence of microstructure and AlPO4 secondary-phase on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid-state electrolyte

NASA Astrophysics Data System (ADS)

Yu, Shicheng; Mertens, Andreas; Gao, Xin; Gunduz, Deniz Cihan; Schierholz, Roland; Benning, Svenja; Hausen, Florian; Mertens, Josef; Kungl, Hans; Tempel, Hermann; Eichel, Rüdiger-A.

2016-09-01

A ceramic solid-state electrolyte of lithium aluminum titanium phosphate with the composition of Li1.3Al0.3Ti1.7(PO4)3 (LATP) was synthesized by a sol-gel method using a pre-dissolved Ti-source. The annealed LATP powders were subsequently processed in a binder-free dry forming method and sintered under air for the pellet preparation. Phase purity, density, microstructure as well as ionic conductivity of the specimen were characterized. The highest density (2.77gṡcm-3) with an ionic conductivity of 1.88×10-4 Sṡcm-1 (at 30∘C) was reached at a sintering temperature of 1100∘C. Conductivity of LATP ceramic electrolyte is believed to be significantly affected by both, the AlPO4 secondary phase content and the ceramic electrolyte microstructure. It has been found that with increasing sintering temperature, the secondary-phase content of AlPO4 increased. For sintering temperatures above 1000∘C, the secondary phase has only a minor impact, and the ionic conductivity is predominantly determined by the microstructure of the pellet, i.e. the correlation between density, porosity and particle size. In that respect, it has been demonstrated, that the conductivity increases with increasing particle size in this temperature range and density.

Identification of an Actual Strain-Induced Effect on Fast Ion Conduction in a Thin-Film Electrolyte.

PubMed

Ahn, Junsung; Jang, Ho Won; Ji, Hoil; Kim, Hyoungchul; Yoon, Kyung Joong; Son, Ji-Won; Kim, Byung-Kook; Lee, Hae-Weon; Lee, Jong-Ho

2018-05-09

Strain-induced fast ion conduction has been a research area of interest for nanoscale energy conversion and storage systems. However, because of significant discrepancies in the interpretation of strain effects, there remains a lack of understanding of how fast ionic transport can be achieved by strain effects and how strain can be controlled in a nanoscale system. In this study, we investigated strain effects on the ionic conductivity of Gd 0.2 Ce 0.8 O 1.9-δ (100) thin films under well controlled experimental conditions, in which errors due to the external environment could not intervene during the conductivity measurement. In order to avoid any interference from perpendicular-to-surface defects, such as grain boundaries, the ionic conductivity was measured in the out-of-plane direction by electrochemical impedance spectroscopy analysis. With varying film thickness, we found that a thicker film has a lower activation energy of ionic conduction. In addition, careful strain analysis using both reciprocal space mapping and strain mapping in transmission electron microscopy shows that a thicker film has a higher tensile strain than a thinner film. Furthermore, the tensile strain of thicker film was mostly developed near a grain boundary, which indicates that intrinsic strain is dominant rather than epitaxial or thermal strain during thin-film deposition and growth via the Volmer-Weber (island) growth mode.

Large optical conductivity of Dirac semimetal Fermi arc surface states

NASA Astrophysics Data System (ADS)

Shi, Li-kun; Song, Justin C. W.

2017-08-01

Fermi arc surface states, a hallmark of topological Dirac semimetals, can host carriers that exhibit unusual dynamics distinct from that of their parent bulk. Here we find that Fermi arc carriers in intrinsic Dirac semimetals possess a strong and anisotropic light-matter interaction. This is characterized by a large Fermi arc optical conductivity when light is polarized transverse to the Fermi arc; when light is polarized along the Fermi arc, Fermi arc optical conductivity is significantly muted. The large surface spectral weight is locked to the wide separation between Dirac nodes and persists as a large Drude weight of Fermi arc carriers when the system is doped. As a result, large and anisotropic Fermi arc conductivity provides a novel means of optically interrogating the topological surfaces states of Dirac semimetals.

Ionic Conduction in Nanocrystalline Materials

DTIC Science & Technology

2000-02-10

In the following, we review studies performed films prepared by a polymer precursor process on on stabilized zirconia ceramics with grain sizes alumina ... titania , is reviewed. While it remains too early to make firm conclusions, the following observations are made. Additives which contribute to ion blocking...Keywords: Ionic conductivity; Nanocrystalline; Zirconia; Ceria; Titania ; Defects 1. Introduction tivity by nearly two orders of magnitude [6]. Given the

Ion transport with charge-protected and non-charge-protected cations using the compensated Arrhenius formalism. Part 2. Relationship between ionic conductivity and diffusion.

PubMed

Petrowsky, Matt; Fleshman, Allison; Bopege, Dharshani N; Frech, Roger

2012-08-09

Temperature-dependent ionic conductivities and cation/anion self-diffusion coefficients are measured for four electrolyte families: TbaTf-linear primary alcohols, LiTf-linear primary alcohols, TbaTf-n-alkyl acetates, and LiTf-n-alkyl acetates. The Nernst-Einstein equation does not adequately describe the data. Instead, the compensated Arrhenius formalism is applied to both conductivity and diffusion data. General trends based on temperature and alkyl chain length are observed when conductivity is plotted against cation or anion diffusion coefficient, but there is no clear pattern to the data. However, plotting conductivity exponential prefactors against those for diffusion results in four distinct curves, one each for the alcohol and acetate families described above. Furthermore, the TbaTf-alcohol and TbaTf-acetate data are "in line" with each other. The conductivity prefactors for the LiTf-alcohol data are smaller than those for the TbaTf data. The LiTf-acetate data have the lowest conductivity prefactors. This trend in prefactors mirrors the observed trend in degree of ionic association for these electrolytes.

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts.

PubMed

Tripathy, Satya N; Wojnarowska, Zaneta; Knapik, Justyna; Shirota, Hideaki; Biswas, Ranjit; Paluch, Marian

2015-05-14

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10(-1)-10(6) Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai's coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

High Conductivity, High Strength Solid Electrolytes Formed by in Situ Encapsulation of Ionic Liquids in Nanofibrillar Methyl Cellulose Networks.

PubMed

Mantravadi, Ramya; Chinnam, Parameswara Rao; Dikin, Dmitriy A; Wunder, Stephanie L

2016-06-01

Strong, solid polymer electrolyte ion gels, with moduli in the MPa range, a capacitance of 2 μF/cm(2), and high ambient ionic conductivities (>1 × 10(-3) S/cm), all at room temperature, have been prepared from butyl-N-methyl pyrrolidinium bis(trifluoromethylsulfonyl) imide (PYR14TFSI) and methyl cellulose (MC). These properties are particularly attractive for supercapacitor applications. The ion gels are prepared by codissolution of PYR14TFSI and MC in N,N-dimethylformamide (DMF), which after heating and subsequent cooling form a gel. Evaporation of DMF leave thin, flexible, self-standing ion gels with up to 97 wt % PYR14TFSI, which have the highest combined moduli and ionic conductivity of ion gels to date, with an excellent electrochemical stability window (5.6 V). These favorable properties are attributed to the immiscibility of PYR14TFSI in MC, which permits the ionic conductivity to be independent of the MC at low MC content, and the in situ formation of a volume spanning network of semicrystalline MC nanofibers, which have a high glass transition temperature (Tg = 190 °C) and remain crystalline until they degrade at 300 °C.

Preparation and electrochemical characterization of ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-based lithium-ion battery separators

NASA Astrophysics Data System (ADS)

Liang, Yinzheng; Ji, Liwen; Guo, Bingkun; Lin, Zhan; Yao, Yingfang; Li, Ying; Alcoutlabi, Mataz; Qiu, Yiping; Zhang, Xiangwu

Lithium lanthanum titanate oxide (LLTO)/polyacrylonitrile (PAN) submicron composite fiber-based membranes were prepared by electrospinning dispersions of LLTO ceramic particles in PAN solutions. These ionic-conducting LLTO/PAN composite fiber-based membranes can be directly used as lithium-ion battery separators due to their unique porous structure. Ionic conductivities were evaluated after soaking the electrospun LLTO/PAN composite fiber-based membranes in a liquid electrolyte, 1 M lithium hexafluorophosphate (LiPF 6) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). It was found that, among membranes with various LLTO contents, 15 wt.% LLTO/PAN composite fiber-based membranes provided the highest ionic conductivity, 1.95 × 10 -3 S cm -1. Compared with pure PAN fiber membranes, LLTO/PAN composite fiber-based membranes had greater liquid electrolyte uptake, higher electrochemical stability window, and lower interfacial resistance with lithium. In addition, lithium//1 M LiPF 6/EC/EMC//lithium iron phosphate cells containing LLTO/PAN composite fiber-based membranes as the separator exhibited high discharge specific capacity of 162 mAh g -1 and good cycling performance at 0.2 C rate at room temperature.

Assimilation of NH₄Br in Polyvinyl Alcohol/Poly(N-vinyl pyrrolidone) Polymer Blend-Based Electrolyte and Its Effect on Ionic Conductivity.

PubMed

Parameswaran, V; Nallamuthu, N; Devendran, P; Manikandan, A; Nagarajan, E R

2018-06-01

Biodegradable polymer blend electrolyte based on ammonium based salt in variation composition consisting of PVA:PVP were prepared by using solution casting technique. The obtained films have been analyzed by various technical methods like as XRD, FT-IR, TG-DSC, SEM analysis and impedance spectroscopy. The XRD and FT-IR analysis exposed the amorphous nature and structural properties of the complex formation between PVA/PVP/NH4Br. Impedance spectroscopy analysis revealed the ionic conductivity and the dielectric properties of PVA/PVP/NH4Br polymer blend electrolyte films. The maximum ionic conductivity was determined to be 6.14 × 10-5 Scm-1 for the composition of 50%PVA: 50%PVP: 10% NH4Br with low activation energy 0.3457 eV at room temperature. Solid state battery is fabricated using highest ionic conducting polymer blend as electrolyte with the configuration Zn/ZnSO4 · 7H2O (anode) ∥ 50%PVA: 50%PVP: 10% NH4Br ∥ Mn2O3 (cathode). The observed open circuit voltage is 1.2 V and its performance has been studied.

Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

PubMed

Sadeghi, Rahmat; Ebrahimi, Nosaibah

2011-11-17

A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are interpreted in terms of ion association, ion-dipole interactions, and structural factors of the ionic liquid and investigated organic solvents. The ionic liquid is solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation.

New generation Li+ NASICON glass-ceramics for solid state Li+ ion battery applications

NASA Astrophysics Data System (ADS)

Sharma, Neelakshi; Dalvi, Anshuman

2018-04-01

Lithiumion conducting NASICON glass-ceramics have been prepared by a novel planetary ball milling assisted synthesis route. Structural, thermal and electrical investigations have been carried out on the novel composites composed of LiTi(PO4)3 (LTP) and 50[Li2SO4]-50[Li2O-P2O5] ionic glass reveal interesting results. Composites were prepared keeping the concentration of the ionic glass fixed at 20 wt%. X-ray diffraction and diffe rential thermal analysis confirm the glass-ceramic formation. Moreover, the structure of LTP remains intact during the glass -ceramic formation. Electrical conductivity of the glass-ceramic composite is found to be higher than that of the pristine glass (50LSLP) and LTP. The bulk and grain boundary conductivities of LTP exhibit improvement in composite. Owing to high ionic conductivity and thermal stability, novel glass -ceramic seems to be a promising candidate for all solid-state battery applications.

Design principles for solid-state lithium superionic conductors.

PubMed

Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand

2015-10-01

Lithium solid electrolytes can potentially address two key limitations of the organic electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochemical stability. However, achieving a Li(+) conductivity in the solid state comparable to existing liquid electrolytes (>1 mS cm(-1)) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centred cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic conductivity, and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.

Water uptake, ionic conductivity and swelling properties of anion-exchange membrane

NASA Astrophysics Data System (ADS)

Duan, Qiongjuan; Ge, Shanhai; Wang, Chao-Yang

2013-12-01

Water uptake, ionic conductivity and dimensional change of the anion-exchange membrane made by Tokuyama Corporation (A201 membrane) are investigated at different temperatures and water activities. Specifically, the amount of water taken up by membranes exposed to water vapor and membranes soaked in liquid water is determined. The water uptake of the A201 membrane increases with water content as well as temperature. In addition, water sorption data shows Schroeder's paradox for the AEMs investigated. The swelling properties of the A201 membrane exhibit improved dimensional stability compared with Nafion membrane. Water sorption of the A201 membrane occurs with a substantial negative excess volume of mixing. The threshold value of hydrophilic fraction in the A201 membrane for ionic conductivity is around 0.34, above which, the conductivity begins to rise quickly. This indicates that a change in the connectivity of the hydrophilic domains occurs when hydrophilic fraction approaches 0.34.

Electronically and ionically conductive porous material and method for manufacture of resin wafers therefrom

DOEpatents

Lin, YuPo J [Naperville, IL; Henry, Michael P [Batavia, IL; Snyder, Seth W [Lincolnwood, IL

2011-07-12

An electrically and ionically conductive porous material including a thermoplastic binder and one or more of anion exchange moieties or cation exchange moieties or mixtures thereof and/or one or more of a protein capture resin and an electrically conductive material. The thermoplastic binder immobilizes the moieties with respect to each other but does not substantially coat the moieties and forms the electrically conductive porous material. A wafer of the material and a method of making the material and wafer are disclosed.

Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy.

PubMed

Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil

2016-04-04

Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

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

New Pyrazolium Salts as a Support for Ionic Liquid Crystals and Ionic Conductors.

PubMed

Pastor, María Jesús; Sánchez, Ignacio; Campo, José A; Schmidt, Rainer; Cano, Mercedes

2018-04-03

Ionic liquid crystals (ILCs) are a class of materials that combine the properties of liquid crystals (LCs) and ionic liquids (ILs). This type of materials is directed towards properties such as conductivity in ordered systems at different temperatures. In this work, we synthesize five new families of ILCs containing symmetrical and unsymmetrical substituted pyrazolium cations, with different alkyl long-chains, and anions such as Cl - , BF₄ - , ReO₄ - , p -CH₃-₆H₄SO₃ - (PTS) and CF₃SO₃ - (OTf). We study their thermal behavior by polarized light optical microscopy (POM) and differential scanning calorimetry (DSC). All of them, except those with OTf as counteranion, show thermotropic mesomorphism. The observations by POM reveal textures of lamellar mesophases. Those agree with the arrangement observed in the X-ray crystal structure of [H₂pz R(4),R(4) ][ReO₄]. The nature of the mesophases is also confirmed by variable temperature powder X-ray diffraction. On the other hand, the study of the dielectric properties at variable temperature in mesomorphic (Cl - and BF₄ - ) and non-mesomorphic (OTf) salts indicates that the supramolecular arrangement of the mesophase favors a greater ionic mobility and therefore ionic conductivity.

High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

PubMed

Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

2011-08-07

Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid Alkali Metal Salts in Polyethylene Oxide * Redox Behavior of Alkyl Viologens in Ion Conductive Polymer Solid * Ionic Conductivity of Interpenetrating Polymer Networks Containing LiClO4 * Electrochemical Behaviors of Porphyrins Incorporated into Solid Polymer Electrolytes * Lithium Ion Conducting Polymer Electrolytes * Electrochemical Synthesis of Polyaniline Thin Film * Electrochemical Aspect of Polyaniline Electrode in Aqueous Electrolyte * Mixed Cation Effect in Epoxy Resin - PEO-IPN Containing Perchlorate Salts * Conductivity, Raman and IR Studies on the Doped PEO-PPG Polymer Blends * Proton Conducting Polymeric Electrolytes from Poly (Ethyleneoxide) System * Surface Structure of Polymer Solid Ionic Conductors Based on Segmented Polyether Polyurethaneureas * Study on Addition Products of LiI and Diethylene Glycol etc. * Solid State Rechargeable Battery Using Paper Form Copper Ion Conductive Solid Electrolyte * Characterization of Electrode/Electrolyte Interfaces in Battery Li/PVAC-Li-Mont./Li1+xV3O8 by AC Impedance Method * Investigation on Reversibility of Vanadium Oxide Cathode Materials in Solid-State Battery * Preparation and Characterization of Silver Boromolybdate Solid State Batteries * The Electric Properties of the Trinary Cathode Material and its Application in Magnisium Solid State Cell * Electrical Properties and Phase Relation of Na2Mo0.1S0.9O4 Doped with Rare Earth Sulfate * New Electrochemical Probe for Rapid Determination of Silicon Concentration in Hot Metals * A New Theoretical EMF Expression for SOx(x = 2, 3) Sensors Based on Na2SO4 Solid Electrolyte * Evaluation of the Electrochemical SOx(x = 2, 3) Sensor with a Tubular Nasicon Electrolyte * The Response Time of a Modified Oxygen Sensor Using Zirconia Electrolyte * Preparation, Characteristics and Sintering Behavior of MgO-PSZ Powder * Reaction between La0.9MnO3 and Yttria Doped Zirconia * Development of the Extended-Life Oxygen Sensor of Caβ''-Al2O3 * Caβ''-Al2O3 Ultra-Low Oxygen Sensor * Measurement of Sulfur Concentration with Zirconia-Based Electrolyte Cell in Molten Iron * Influence of SO2 on the Conductivity of Calcia Stabilized Zirconia * Reactions between YSZ and La1-xCaxMnO3 as a Cathode for SOFC * Preparation and Electrical Properties of Lithium β''-Alumina * Influence of Lithia Content on Properties of β''-Alumina Ceramics * Electrical Conductivity of Solid Solutions of Na2SO4 with Na2SeO4 * Effect of Antagonist XO42- = MoO42- and WO42- Ion Substitution on the Electrical Conductivity of Li2SO4 : Li2CO3 Eutectic System * Study on the Electrical Properties and Structure of Multicrystal Materials Li5+xGe1-xCrxV3O12 * Preliminary Study on Synthesis of Silver Zirconium Silicophosphates by Sol - Gel Process * Sodium Ion Conduction in Iron(III) Exchanged Y Zeolite * Electrical Properties of V5O9+x (x = 0, 1) and CuxV5O9.1 * Electrical Properties of the Tetragonal ZrO2 Stabilized with CeO2, CeO2 + Gd2O3 * Study of Preparation and Ionic Conduction of Doped Barium Cerate Perovskite * Preparing Fine Alumina Powder by Homogeneous Precipitation Method for Fabricating β''-Al2O3 * Amorphous Lithium Ion Conductors in Li2S-SiS2-LiBO2 System * Mixed Alkali Effect of Glass Super Ionic Conductors * Electrical Property and Phase Separation, Crystallization Behavior of A Cu+-Conducting Glass * Investigation of Phase Separation and Crystallization for 0.4CuI-0.3 Cu2O-0.3P2O5 Glass by SEM and XRD * Study on the Lithium Solid Electrolytes of Li3N-LiX(X = F, Cl, Br, I)-B2O3 Ternary Systems * Synthesis and Characterization of the Li2O : P2O5 : WO3 Glasses * The Electrochromic Properties of Electrodeposited Ni-O Films in Nonaqueous Electrolytes * All Solid-State WO3-MnO2 Based Electrochromic Window * Electrochromism in Nickel Oxide Films * E S R of X-Irradiated Melt Quenched Li2SO4 * Mixed-Alkali Effect in the Li2O-Na2O-TeO2 Glass System * Electrical and Thermal Studies on Silver Tellurite Glasses * Late Entries (Invited Papers) * Proton Conducting Polymers * Light Scattering Studies on Superionic Conductor YSZ * Development of Thin Film Surface Modified Solid State Electrochemical Gas Sensors * Author Index * List of Participants

Field determination of the three-dimensional hydraulic conductivity tensor of anisotropic media: 2. Methodology and application to fractured rocks

USGS Publications Warehouse

Hsieh, Paul A.; Neuman, Shlomo P.; Stiles, Gary K.; Simpson, Eugene S.

1985-01-01

The analytical solutions developed in the first paper can be used to interpret the results of cross-hole tests conducted in anisotropic porous or fractured media. In the particular case where the injection and monitoring intervals are short relative to the distance between them, the test results can be analyzed graphically. From the transient variation of hydraulic head in a given monitoring interval, one can determine the directional hydraulic diffusivity, Kd(e)/Ss, and the quantity D/Ss, by curve matching. (Here Kd(e) is directional hydraulic conductivity parallel to the unit vector, e, pointing from the injection to the monitoring interval, Ss is specific storage, and D is the determinant of the hydraulic conductivity tensor, K.) The principal values and directions of K, together with Ss, can then be evaluated by fitting an ellipsoid to the square roots of the directional diffusivities. Ideally, six directional measurements are required. In practice, a larger number of measurements is often necessary to enable fitting an ellipsoid to the data by least squares. If the computed [Kd(e)/ss]½ values fluctuate so severely that a meaningful least squares fit is not possible, one has a direct indication that the subsurface does not behave as a uniform anisotropic medium on the scale of the test. Test results from a granitic rock near Oracle in southern Arizona are presented to illustrate how the method works for fractured rocks. At the site, the Oracle granite is shown to respond as a near-uniform, anisotropic medium, the hydraulic conductivity of which is strongly controlled by the orientations of major fracture sets. The cross-hole test results are shown to be consistent with the results of more than 100 single-hole packer tests conducted at the site.

Super ionic conductive glass

DOEpatents

Susman, Sherman; Volin, Kenneth J.

1984-01-01

An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

Lithium-Air and ionic Liquids

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

Kellar, Michael

2015-09-01

The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to themore » typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.« less

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Ion transferring in polyelectrolyte networks in electric fields

NASA Astrophysics Data System (ADS)

Li, Honghao; Erbas, Aykut; Zwanikken, Jos; Olvera de La Cruz, Monica

Ion-conducting polyelectrolyte gels have drawn the attention of many researchers in the last few decades as they have wide applications not only in lithium batteries but also as stretchable, transparent ionic conductor or ionic cables devices. However, ion dynamics in polyelectrolyte gels has been much less studied analytically or computationally due to the complicated interplay of long-range electrostatic and short-range interactions. Here we propose a coarse-grained non-equilibrium molecular dynamics simulation to study the ion dynamics in polyelectrolyte gels under external electric fields. We found a nonlinear response region where the molar conductivity of polyelectrolyte gels increases with external fields. We propose counterion redistribution under electric fields as the driving mechanism. We also found the ionic conductivity to be modulated by changing polylelectrolyte network topology such as the chain length. Our discovery reveals the essential difference of ion dynamics between electrolytes and polyelectrolyte gels. These results will expand our understanding in charged polymeric systems and help in designing ion-conducting devices with higher conductivity.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments.

PubMed

Emerson, H P; Zengotita, F; Richmann, M; Katsenovich, Y; Reed, D T; Dittrich, T M

2018-10-01

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium K d 's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects on RCS of a perfect electromagnetic conductor sphere in the presence of anisotropic plasma layer

NASA Astrophysics Data System (ADS)

Ghaffar, A.; Hussan, M. M.; Illahi, A.; Alkanhal, Majeed A. S.; Ur Rehman, Sajjad; Naz, M. Y.

2018-01-01

Effects on RCS of perfect electromagnetic conductor (PEMC) sphere by coating with anisotropic plasma layer are studied in this paper. The incident, scattered and transmitted electromagnetic fields are expanded in term of spherical vector wave functions using extended classical theory of scattering. Co and cross-polarized scattered field coefficients are obtained at the interface of free space-anisotropic plasma and at anisotropic plasma-PEMC sphere core by scattering matrices method. The presented analytical expressions are general for any perfect conducting sphere (PMC, PEC, or PEMC) with general anisotropic/isotropic material coatings that include plasma and metamaterials. The behavior of the forward and backscattered radar cross section of PEMC sphere with the variation of the magnetic field strength, incident frequency, plasma density, and effective collision frequency for the co-polarized and the cross polarized fields are investigated. It is also observed from the obtained results that anisotropic layer on PEMC sphere shows reciprocal behavior as compared to isotopic plasma layer on PEMC sphere. The comparisons of the numerical results of the presented analytical expressions with available results of some special cases show the correctness of the analysis.

A second-order 3D electromagnetics algorithm for curved interfaces between anisotropic dielectrics on a Yee mesh

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

Bauer, Carl A., E-mail: bauerca@colorado.ed; Werner, Gregory R.; Cary, John R.

A new frequency-domain electromagnetics algorithm is developed for simulating curved interfaces between anisotropic dielectrics embedded in a Yee mesh with second-order error in resonant frequencies. The algorithm is systematically derived using the finite integration formulation of Maxwell's equations on the Yee mesh. Second-order convergence of the error in resonant frequencies is achieved by guaranteeing first-order error on dielectric boundaries and second-order error in bulk (possibly anisotropic) regions. Convergence studies, conducted for an analytically solvable problem and for a photonic crystal of ellipsoids with anisotropic dielectric constant, both show second-order convergence of frequency error; the convergence is sufficiently smooth that Richardsonmore » extrapolation yields roughly third-order convergence. The convergence of electric fields near the dielectric interface for the analytic problem is also presented.« less

Method to detect the end-point for PCR DNA amplification using an ionically labeled probe and measuring impedance change

DOEpatents

Miles, Robin R [Danville, CA; Belgrader, Phillip [Severna Park, MD; Fuller, Christopher D [Oakland, CA

2007-01-02

Impedance measurements are used to detect the end-point for PCR DNA amplification. A pair of spaced electrodes are located on a surface of a microfluidic channel and an AC or DC voltage is applied across the electrodes to produce an electric field. An ionically labeled probe will attach to a complementary DNA segment, and a polymerase enzyme will release the ionic label. This causes the conductivity of the solution in the area of the electrode to change. This change in conductivity is measured as a change in the impedance been the two electrodes.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors

NASA Astrophysics Data System (ADS)

Marple, M. A. T.; Avila-Paredes, H.; Kim, S.; Sen, S.

2018-05-01

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors.

PubMed

Marple, M A T; Avila-Paredes, H; Kim, S; Sen, S

2018-05-28

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Impedance analysis on PVA/PVP: GO blend nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Rao, M. C.; Basha, S. K. Shahenoor; Kumar, B. Ranjit

2018-05-01

Nanocomposite polymer films have been prepared by doping Graphene oxide (GO) in PVA/PVP blend polymers by solution cast technique. AC conductivity studies were performed on to the prepared nanocomposite films and the maximum ionic conductivity is found to be 6.13x10-4 Scm-1 for (0.30:0.3) wt% of nanocomposite polymer film at room temperature. The maximum ionic conductivity of nanocomposite polymer films of PVA/PVP: GO holds great promise in potential applications.

Biologically Inspired, Anisoptropic Flexible Wing for Optimal Flapping Flight

DTIC Science & Technology

2013-01-31

Anisotropic Flexible Wing for Optimal Flapping Flight FA9550-07-1-0547 Sb. GRANT NUMBER Sc. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Sd. PROJECT NUMBER...anisotropic structural flexibility ; c) Conducted coordinated experimental and computational modeling to determine the roles of aerodynamic loading, wing inertia...and structural flexibility and elasticity; and d) Developed surrogate tools for flapping wing MA V design and optimization. Detailed research

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

Nanofiber Anisotropic Conductive Films (ACF) for Ultra-Fine-Pitch Chip-on-Glass (COG) Interconnections

NASA Astrophysics Data System (ADS)

Lee, Sang-Hoon; Kim, Tae-Wan; Suk, Kyung-Lim; Paik, Kyung-Wook

2015-11-01

Nanofiber anisotropic conductive films (ACF) were invented, by adapting nanofiber technology to ACF materials, to overcome the limitations of ultra-fine-pitch interconnection packaging, i.e. shorts and open circuits as a result of the narrow space between bumps and electrodes. For nanofiber ACF, poly(vinylidene fluoride) (PVDF) and poly(butylene succinate) (PBS) polymers were used as nanofiber polymer materials. For PVDF and PBS nanofiber ACF, conductive particles of diameter 3.5 μm were incorporated into nanofibers by electrospinning. In ultra-fine-pitch chip-on-glass assembly, insulation was significantly improved by using nanofiber ACF, because nanofibers inside the ACF suppressed the mobility of conductive particles, preventing them from flowing out during the bonding process. Capture of conductive particles was increased from 31% (conventional ACF) to 65%, and stable electrical properties and reliability were achieved by use of nanofiber ACF.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

DOE PAGES

Lin, Ye; Fang, Shumin; Su, Dong; ...

2015-04-10

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study

NASA Astrophysics Data System (ADS)

Weyman, Alexander; Bier, Markus; Holm, Christian; Smiatek, Jens

2018-05-01

We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids. The ion transport numbers are unaffected by the occurrence of these domains, and the corresponding values highlight the potential role of PILs as single-ion conductors in electrochemical devices. In contrast to bulk behavior, a pronounced formation of ion conductivity channels in confined systems is initiated in close vicinity to the boundaries. We observe higher ion conductivities in these channels for increasing PIL side chain lengths in comparison with bulk values and provide an explanation for this effect. The appearance of these domains points to an improved application of PILs in modern polymer electrolyte batteries.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

PubMed Central

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-01-01

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2−δ–CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2−δ–Ce0.8Gd0.2O2−δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution. PMID:25857355

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

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

Lin, Ye; Fang, Shumin; Su, Dong

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

Ionic-Electronic Ambipolar Transport in Metal Halide Perovskites: Can Electronic Conductivity Limit Ionic Diffusion?

PubMed

Kerner, Ross A; Rand, Barry P

2018-01-04

Ambipolar transport describes the nonequilibrium, coupled motion of positively and negatively charged particles to ensure that internal electric fields remain small. It is commonly invoked in the semiconductor community where the motion of excess electrons and holes drift and diffuse together. However, the concept of ambipolar transport is not limited to semiconductor physics. Materials scientists working on ion conducting ceramics understand ambipolar transport dictates the coupled diffusion of ions and the rate is limited by the ion with the lowest diffusion coefficient. In this Perspective, we review a third application of ambipolar transport relevant to mixed ionic-electronic conducting materials for which the motion of ions is expected to be coupled to electronic carriers. In this unique situation, the ambipolar diffusion model has been successful at explaining the photoenhanced diffusion of metal ions in chalcogenide glasses and other properties of materials. Recent examples of photoenhanced phenomena in metal halide perovskites are discussed and indicate that mixed ionic-electronic ambipolar transport is similarly important for a deep understanding of these emerging materials.

Nanomechanical measurements of ionic effect on nanoconfined water

NASA Astrophysics Data System (ADS)

Kramkowski, Edward; Khan, Shah; Hoffmann, Peter

2015-03-01

The behavior of liquid molecules confined to nanometer-scale spaces is a topic of particular interest to a variety of fields. From lab-on-a-chip medical device manufacturers to petroleum engineers involved in oil recovery, a wide range of researchers could benefit from a better understanding of the mechanics of nanoconfined liquids. Previous research has shown that above a critical strain rate, a confined liquid exhibits a solid-like response that oscillates with a period roughly equal to the molecular diameter of the liquid being observed. This indicates that when a liquid is compressed at a rate faster than the molecules can diffuse in bulk out from between the confining surfaces, it dynamically solidifies into an anisotropic layered liquid. In order to better understand the influence that the confining surfaces have on this behavior, we have been observing how the addition of different classes of ions at varying concentrations to a pure water sample either enhance or suppress the natural tendency of the water to order. The work indicates that an ion's effect on the liquid's structure is commensurate with its classification according to the Hofmeister series, with the amount of deviation from the pure behavior governed by the ionic concentration.

Ionic conductors for solid oxide fuel cells

DOEpatents

Krumpelt, Michael; Bloom, Ira D.; Pullockaran, Jose D.; Myles, Kevin M.

1993-01-01

An electrolyte that operates at temperatures ranging from 600.degree. C. to 800.degree. C. is provided. The electrolyte conducts charge ionically as well as electronically. The ionic conductors include molecular framework structures having planes or channels large enough to transport oxides or hydrated protons and having net-positive or net-negative charges. Representative molecular framework structures include substituted aluminum phosphates, orthosilicates, silicoaluminates, cordierites, apatites, sodalites, and hollandites.

A novel bio electro active alginate-aniline tetramer/ agarose scaffold for tissue engineering: synthesis, characterization, drug release and cell culture study.

PubMed

Atoufi, Zhale; Zarrintaj, Payam; Motlagh, Ghodratollah Hashemi; Amiri, Anahita; Bagher, Zohreh; Kamrava, Seyed Kamran

2017-10-01

In this study, synthesis of a novel biocompatible stimuli-responsive conducting hydrogel based on agarose/alginate-aniline tetramer with the capability of a tailored electrically controlled drug-release for neuroregeneration is investigated. First, aniline tetramer is synthesized and grafted onto sodium alginate. Then, this material is added to agarose as an electrical conductivity modifier to obtain Agarose/alginate-aniline tetramer hydrogel. The synthesized materials are characterized by H NMR and FTIR. The hydrogels are prepared with varying content of aniline tetramer and their swelling-deswelling and shape memory behavior is evaluated. The electroactivity and ionic conductivity of hydrogels against temperature is measured. The sample with 10% aniline tetramer (AT10) reveals the highest ionic conductivity. In MTT and SEM assays, AT10 shows the best cell viability and cell proliferation due to its highest ionic conductivity highlighting the fact that electrical stimuli cell signaling. Hydrogels also represent great potentials for passive and electro-stimulated dexamethasone release. These results demonstrate that the newly developed conducting hydrogels are promising materials for neuroregenerative medicine.

Superionic Conductivity of Sm3+, Pr3+, and Nd3+ Triple-Doped Ceria through Bulk and Surface Two-Step Doping Approach.

PubMed

Liu, Yanyan; Fan, Liangdong; Cai, Yixiao; Zhang, Wei; Wang, Baoyuan; Zhu, Bin

2017-07-19

Sufficiently high oxygen ion conductivity of electrolyte is critical for good performance of low-temperature solid oxide fuel cells (LT-SOFCs). Notably, material conductivity, reliability, and manufacturing cost are the major barriers hindering LT-SOFC commercialization. Generally, surface properties control the physical and chemical functionalities of materials. Hereby, we report a Sm 3+ , Pr 3+ , and Nd 3+ triple-doped ceria, exhibiting the highest ionic conductivity among reported doped-ceria oxides, 0.125 S cm -1 at 600 °C. It was designed using a two-step wet-chemical coprecipitation method to realize a desired doping for Sm 3+ at the bulk and Pr 3+ /Nd 3+ at surface domains (abbreviated as PNSDC). The redox couple Pr 3+ /Pr 4+ contributes to the extraordinary ionic conductivity. Moreover, the mechanism for ionic conductivity enhancement is demonstrated. The above findings reveal that a joint bulk and surface doping methodology for ceria is a feasible approach to develop new oxide-ion conductors with high impacts on advanced LT-SOFCs.

Mecanismes de deformation de nanoparticules d'Au par irradiation ionique

NASA Astrophysics Data System (ADS)

Harkati Kerbouah, Chahineze

2011-12-01

In the present thesis, we study the anisotropic deformation of gold nanoparticles embedded in amorphous silica or crystalline aluminum arsenide, under ion bombardment. We try to comprehend the mechanism responsible for this deformation and to remove any ambiguity related to the explanation of this phenomenon. A hybrid process combining sputtering and plasma enhanced chemical vapour deposition was used to fabricate Au/SiO2 layers on fused silica substrates. Structures with single and multilayer were obtained. Heating during or after deposition activates the Au atom agglomeration and favours the growth of the nanoparticles. Also, a Au/AlAs nanocomposite was obtained by ion implantation of AlAs films, followed by rapid thermal annealing. The samples of the two nanocomposites, cooled with liquid nitrogen, were irradiated with 2 to 40 MeV Cu, Si, Au or In ion beams, at fluences ranging from 1x10 13 to 4x1015 ions/cm2, using a Tandem or Tandetron accelerator. The structural and morphological properties of the Au/SiO2 nanocomposite were extracted by optical means; the frequency and the width of surface plasmon resonance band depend on the nanoparticle shape and size, their concentration, the inter-particle distance and the dielectric properties of material in which the particles are embedded. The aluminum arsenide crystallinity was studied by two techniques: Raman spectroscopy and Rutherford backscattering spectrometry in channelling configuration (RBS/ channelling). The Au concentration in the nanocomposite layers was deducted from RBS results. The size distribution and metallic nanoparticles shape transformation in both nanocomposites were observed by electronic transmission microscopy. The results obtained within the framework of this work are the subject of three journal papers. The first publication shows the possibility of manipulating the width and spectral position of the gold nanoparticle absorption band in Au/SiO2 nanocomposites by modifying their structure (form, size and inter-particle distance). The obtained Au nanoparticles are nearly spherical. The surface plasmon (PS) absorption band corresponding to the distant particles is located at 520 nm. After ion irradiation, the spherical nanoparticles transform into ellipsoids aligned along the ion beam. The absorption band splits into two bands: transversal and longitudinal. The band corresponding to the ellipsoids small axis (transversal) is blue-shifted and that corresponding to the long axis (longitudinal) is red-shifted indicating the elongation of particles in the beam direction. The second paper is consecrated to the crucial role of the plastic deformation of the matrix and to the importance of the metal atomic mobility in the anisotropic nanoparticles deformation in Au/SiO 2 nanocomposites. Our measurements show that a threshold value of 2 keV/nm (electronic stopping power) is necessary for the deformation of Au nanoparticles. This value is close to that required for silica deformation. Mobility of the Au atoms at the time of the ion passage is confirmed by temperature calculation within the ionic track. The third paper treats the attempt of formation and deformation of Au nanoparticles in crystalline aluminum arsenide matrix known by its high resistance to amorphisation and deformation under ionic bombardment. The principal result of the last article confirms the essential role of the matrix. It proves that the anisotropic deformation of surrounding material is indispensable for gold nanoparticles deformation. The experimental results mentioned above and temperature calculations within ionic tracks allowed us to propose the following anisotropic deformation scenario of Au nanoparticles embedded in Au/SiO2 nanocomposite: (1) Each ion crossing the silica melts (very briefly) a narrow cylinder around its trajectory forming thus a latent track. This is consistent with the observed threshold value in the electronic stopping power. (2) The cumulative effect of many separate ion impacts leads to the anisotropic growth of the silica matrix which contracts in the direction of the beam and elongates in the perpendicular direction. The overlap model of the ionic tracks was used to validate this phenomenon. (3) The deformation of silica generates strains which act on the nanoparticles in the plane perpendicular to the ion trajectory. In order to accommodate these strains, the Au nanoparticles deform in the beam direction. (4) The deformation of nanoparticles occurs each time an ion traverses the gold particle and melts a cylinder around its trajectory. The mobility of the gold atoms was confirmed by a calculation of the equivalent temperature from the deposited energy in the material by incident ions. The scenario above is compatible with our experimental data obtained in the case of the Au/SiO2 nanocomposite. It is further supported by the fact that the Au nanoparticules do not deform when they are integrated in AlAs which is resistant to the deformation. Keywords: ion irradiation, nanoparticles, Au, electronic stopping power, surface plasmon resonance, elongation, silica, aluminum arsenide.

Optic phonons and anisotropic thermal conductivity in hexagonal Ge 2Sb 2Te 5

DOE PAGES

Mukhopadhyay, Saikat; Lindsay, Lucas R.; Singh, David

2016-11-16

The lattice thermal conductivity ($κ$) of hexagonal Ge 2Sb 2Tesub>5 (h-GST) is studied via direct first-principles calculations. We find significant intrinsic anisotropy of ( $κ$ a/$κ$ c~2) of $κ$ in bulk h-GST along different transport directions. The dominant contribution to$κ$ is from optic phonons, ~75%. This is extremely unusual as the acoustic phonon modes carry most of the heat in typical semiconductors and insulators with small unit cells. Very recently, Lee et. al. observed anisotropic in GST thin films and attributed this to thermal resistance of amorphous regions near grain boundaries. However, our results suggest an additional strong intrinsic anisotropymore » for the pure hexagonal phase. This derives from bonding anisotropy along different crystal directions, specifically from weak interlayer coupling, which gives anisotropic phonon dispersions. The phonon spectrum of h-GST has very dispersive optic branches with higher group velocities along the a-axis as compared to flat optic bands along the c-axis. The importance of optic mode contributions for the thermal conductivity in low-$κ$ h-GST is unusual, and development of fundamental physical understanding of these contributions may be critical to better understanding of thermal conduction in other complex layered materials.« less

Effects of Polymer Structure and Relaxations on Ionic Conductivity in Anion Exchange Membranes with Quaternary Ammonium Functional Groups

NASA Astrophysics Data System (ADS)

Maes, Ashley M.

Anion exchange membranes (AEMs) are of considerable interest to developers and researchers of electrochemical conversion and storage devices such as anion exchange membrane fuel cells (AAEMFCs), alkaline polymer electrolyte electrolysers, redox flow batteries and bioelectrochemical devices. AEMs are generally in competition with more established proton exchange membranes (PEMs), but offer the potential for reduction of materials costs and greater fuel flexibility across these applications. This work includes an introduction to AEMs in the context of fuel cell technologies and some key techniques for AEM characterization. There are many synthetic strategies to incorporate cationic functional groups, which promote anion transport, into a polymer matrix. Two membrane chemistries are investigated in the following chapters. The first is based on a simple synthesis procedure that produced a membrane consisting of random, crosslinked polypropylene- ran-polyethyleneimine with quaternary ammonium functional groups. This membrane had moderate chloride ionic conductivity of 0.03 S cm -1 at 95 °C and high water uptake with minimal dimensional swelling. However, the lack of control of crosslink location and density during synthesis produced a material with a very random nature, making it a poor candidate for more fundamental transport studies. The second membrane chemistry is a block copolymer with a hydrophobic and hydrophilic block. The hydrophobic block was selected to provide favorable mechanical and barrier characteristics while a hydrophilic block was selected to provide water uptake and anion conducting functionalities. Poly(vinyl benzyl trimethyl ammonium bromide)-b-poly(methylbutylene) ([PVBTMA][Br]- b-PMB) was synthesized by partners at the University of Massachusetts-Amherst with varied degrees of functionalization (DF) along the hydrophilic block, resulting in ion exchange capacities ranging from 0.77 to 2.20 mmol g -1. Water uptake, in-plane ionic conductivity and membrane morphology were measured across a series of membranes with the original bromide (Br -) counter-ion. These bulk materials characterization experiments demonstrated that this polymer structure produces well-ordered lamellar morphology with moderate water uptake and competitive ionic conductivity (ca. 40 mS cm-1 at 90 °C and 95% relative humidity). These characteristics make it an appropriate candidate for the following more fundamental investigations of ionic conductivity mechanisms. Broadband electrical spectroscopy (BES) was conducted on one [PVBTMA][Br]- b-PMB sample in the Br- form and analyzed in conjunction with thermal stability and relaxation experiments in Chapter 4. We were able to propose two separate ionic conductivity mechanisms and relate each to physical attributes of the polymer structure. A significant thermal transition was observed at Tdelta , which resulted in a dramatic drop in conductivity. In a continued effort to characterize the ionic conductivity of these block-copolymer membranes, another BES study was conducted on three samples with varying DFs. Samples were converted to hydroxide (OH- ) form so we could contrast the Br- conductivity mechanisms to those in a more relevant counter-ion form. After analysis of the electric response of the material, combined with the thermal analysis by TGA, MDSC and DMA, conductivity mechanisms were described. As in the Br- study, conductivity involves two distinct conduction pathways, sigmaEP and sigmaIP,1. Importantly, we again observed a drop in conductivity at Tdelta in each of these samples, with Tdelta decreasing as the density of functional groups along the hydrophilic block increased. It is undesirable for this transition to occur during operation in a fuel cell or other electrochemical device, so future work to investigate strategies for inhibition are recommended.

Nonequilibrium Simulations of Ion Dynamics in Ionomer Melts

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. However, to date ionomers do not have sufficiently high conductivities for practical application, most likely because the ions tend to form aggregates, leading to slow ion transport. To build a better understanding of the relationships among ionomer chemistry, morphology, and ion transport, we have performed a series of molecular dynamics simulations and connected aspects of these simulations with experiment. In previous work using both atomistic and coarse-grained models, we showed that precise ionomers (with a fixed spacing between ionic groups along the polymer backbone) exhibit a range of ionic aggregate morphologies, from discrete clusters to percolated aggregates. In this talk I will describe recent simulations of our coarse-grained ionomer melts in an applied electric field. From a constant applied field, we are able to extract the ion mobilities and hence conductivities. We find that ionomers with percolated ionic aggregate morphologies have higher ion mobilities and hence higher conductivities. Application of an oscillating electric field enables us to calculate the frequency-dependent conductivity of the model ionomer melts. The real part of the conductivity has a high frequency peak associated with plasma oscillations, and a very broad low frequency peak associated with ion motions in ionic aggregates. I will end with comments on the connections to atomistic simulations and to experimental probes of ion dynamics. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Synergistic Impacts of Electrolyte Adsorption on the Thermoelectric Properties of Single-Walled Carbon Nanotubes.

PubMed

Nakano, Motohiro; Nakashima, Takuya; Kawai, Tsuyoshi; Nonoguchi, Yoshiyuki

2017-08-01

Single-walled carbon nanotubes are promising candidates for light-weight and flexible energy materials. Recently, the thermoelectric properties of single-walled carbon nanotubes have been dramatically improved by ionic liquid addition; however, controlling factors remain unsolved. Here the thermoelectric properties of single-walled carbon nanotubes enhanced by electrolytes are investigated. Complementary characterization with absorption, Raman, and X-ray photoelectron spectroscopy reveals that shallow hole doping plays a partial role in the enhanced electrical conductivity. The molecular factors controlling the thermoelectric properties of carbon nanotubes are systematically investigated in terms of the ionic functionalities of ionic liquids. It is revealed that appropriate ionic liquids show a synergistic enhancement in conductivity and the Seebeck coefficient. The discovery of significantly precise doping enables the generation of thermoelectric power factor exceeding 460 µW m - 1 K -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of ionic transport in sodium scandium phosphate (NSP) and related compounds

NASA Astrophysics Data System (ADS)

Bhat, Kaustubh; Blügel, Stefan; Lustfeld, Hans

Sodium ionic conductors offer significant advantages for application in large scale energy storage systems. In this study, we investigate the different pathways available for sodium ion conduction in NSP and calculate energy barriers for ionic transport using Density Functional Theory (DFT) and the Nudged Elastic Band Method. We identify the structural parameters that reduce the energy barrier, by calculating the influence of positive and negative external pressure on the energy barrier. Lattice strain can be introduced by cation or anion substitution within the NASICON structure. We substitute the scandium atom with other trivalent atoms such as aluminium and yttrium, and calculate the resulting energy barriers. Sodium thiophosphate (Na3PS4) has previously shown about two orders of magnitude higher ionic conductivity than sodium phosphate (Na3PO4). We investigate the effect of substituting oxygen with sulphur in NSP. We acknowledge discussions with our experimental colleagues F. Tietz and M. Guin toward this work

Electrical Wave Propagation in an Anisotropic Model of the Left Ventricle Based on Analytical Description of Cardiac Architecture

PubMed Central

Pravdin, Sergey F.; Dierckx, Hans; Katsnelson, Leonid B.; Solovyova, Olga; Markhasin, Vladimir S.; Panfilov, Alexander V.

2014-01-01

We develop a numerical approach based on our recent analytical model of fiber structure in the left ventricle of the human heart. A special curvilinear coordinate system is proposed to analytically include realistic ventricular shape and myofiber directions. With this anatomical model, electrophysiological simulations can be performed on a rectangular coordinate grid. We apply our method to study the effect of fiber rotation and electrical anisotropy of cardiac tissue (i.e., the ratio of the conductivity coefficients along and across the myocardial fibers) on wave propagation using the ten Tusscher–Panfilov (2006) ionic model for human ventricular cells. We show that fiber rotation increases the speed of cardiac activation and attenuates the effects of anisotropy. Our results show that the fiber rotation in the heart is an important factor underlying cardiac excitation. We also study scroll wave dynamics in our model and show the drift of a scroll wave filament whose velocity depends non-monotonically on the fiber rotation angle; the period of scroll wave rotation decreases with an increase of the fiber rotation angle; an increase in anisotropy may cause the breakup of a scroll wave, similar to the mother rotor mechanism of ventricular fibrillation. PMID:24817308

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

PubMed

Funke, Klaus

2013-08-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag 2 S and PbF 2 and coined terms such as cation and anion , electrode and electrolyte . In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Solid State Ionics: from Michael Faraday to green energy—the European dimension

PubMed Central

Funke, Klaus

2013-01-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an ‘evolving scheme of materials science’, point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987. PMID:27877585

Conductivity of gel polymer electrolytes doped with solutions of phosphonic acid or protic ionic liquids

NASA Astrophysics Data System (ADS)

Shmukler, Liudmila E.; Fadeeva, Yuliya A.; Glushenkova, Ekaterina V.; Nguyen, Van Thuc; Safonova, Liubov P.

2018-04-01

The proton-conducting gel electrolytes (PCGEs) based on PMMA, PVdF or PVdF-HFP doped with solutions of phosphonic acid or ammonium based protic ionic liquids (PILs) in DMF have been synthesized. Rather high values of the conductivity (10-4-10-3 S cm-1) have been reached at low dopant concentrations (up to 1 mol l-1). The influence of the nature of both polymeric matrix and dopant as well as dopant concentration on the conductivity values was discussed. It was established that the dependence of conductivity on the nature of dopant, but not the polymeric matrix, was more pronounced.

Development of ionic gels using thiol-based monomers in ionic liquid

NASA Astrophysics Data System (ADS)

Ahmed, Kumkum; Naga, Naofumi; Kawakami, Masaru; Furukawa, Hidemitsu

2016-04-01

Ionic gels (IGs) using ionic liquids (ILs) can propose diverse applications in the field of optics, sensors and separation have opened wide prospects in materials science. ILs have attracted remarkable interest for gel polymer electrolytes and batteries based on their useful properties such as non-volatility, non-flammability, a wide electrochemical window, high thermal stability and a high ionic conductivity. The formation of gel in IL media makes it possible to immobilize ILs within organic or inorganic matrices and to take advantage of their unique properties in the solid state, thus eliminating some shortcomings related to shaping and risk of leakage. In this work for the first time we used multifunctional thiol monomers having uniform structure and good compatibility with the IL of our interest. Therefore we focused on developing thiol monomer-based IGs using multifunctional thiol monomers and acrylate crosslinkers utilizing thiol-ene reaction between monomer and crosslinking molecules in an IL medium and characterize their physico-chemical properties like thermal, conductive, mechanical properties etc.. This work has been focused mainly to improve the mechanical strength of IGs and make prospects of IGs in tribology and lubricants.

Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries

DOE PAGES

Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; ...

2014-11-26

A strategy of mixing both an ionic liquid and sulfone is reported to give synergistic effects of reducing viscosity, increasing ionic conductivity, reducing polysulfide dissolution, and improving safety. The mixtures of ionic liquids and sulfones also show distinctly different physicochemical properties, including thermal properties and crystallization behavior. By using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAhg- 1 (second cycle) by using 40% 1.0 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in N-methyl-Npropylpyrrolidinium bis(trifluoromethylsulfonyl)imide with 60% 1.0 M LiTFSI in methylisopropylsulfone in the first cycle. This capacity is slightly lower thanmore » that obtained in pure 1.0 M LiTFSI as the sulfone electrolyte; however, it exhibits excellent cycling stability and remains as high as 655 mAhg 1 even after 50 cycles. This strategy provides a method to alleviate polysulfide dissolution and redox shuttle phenomena, at the same time, with improved ionic conductivity.« less

Guar gum as biosourced building block to generate highly conductive and elastic ionogels with poly(ionic liquid) and ionic liquid.

PubMed

Zhang, Biao; Sudre, Guillaume; Quintard, Guilhem; Serghei, Anatoli; David, Laurent; Bernard, Julien; Fleury, Etienne; Charlot, Aurélia

2017-02-10

In this study, we report on the simple and straightforward preparation of ionogels arising from the addition of guar gum (a plant-based polysaccharide) in a solution of precisely-defined poly(ionic liquid) chains (PIL) in imidazolium-based ionic liquid (IL). The development of intermolecular polar interactions (mainly hydrogen bonds) and topologic chain entanglements induces the formation of physical biohybrid ionogels, whose elastic properties can be easily tuned by varying the composition (up to 30000Pa). The combined presence of guar gum and PIL confers excellent dimensional stability to the ionogels with no IL exudation combined with high thermal properties (up to 310°C). The resulting materials are shown to exhibit gel scattering profiles and high conductivities (> 10 -4 S/cm at 30°C). The benefit linked to the formation of guar/PIL associations in IL medium enables to find a good compromise between the mechanical cohesion and the mobility ensuring the ionic transport. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rational design of mixed ionic and electronic conducting perovskite oxides for solid oxide fuel cell anode materials: A case study for doped SrTiO3

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

Suthirakun, Suwit; Xiao, Guoliang; Ammal, Salai Cheettu

2014-01-01

The effect of p- and n-type dopants on ionic and electronic conductivity of SrTiO3 based perovskites were investigated both computationally and experimentally. Specifically, we performed density functional theory (DFT) calculations of Na- and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 systems. Constrained ab initio thermodynamic calculations were used to evaluate the phase stability and reducibility of doped SrTiO3 under both oxidizing and reducing synthesis conditions, as well as under anodic solid oxide fuel cell (SOFC) conditions. The density of states (DOS) of these materials was analyzed to study the effects of p- and n-doping on the electronic conductivity. Furthermore, Na-more » and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 samples were experimentally prepared and the conductivity was measured to confirm our computational predictions. The experimental observations are in very good agreement with the theoretical predictions that doping n-doped SrTiO3 with small amounts of p-type dopants promotes both the ionic and electronic conductivity of the material. This doping strategy is valid independent of p- and n-doping site and permits the synthesis of perovskite based mixed ionic/electronic conductors.« less

Super ionic conductive glass

DOEpatents

Susman, S.; Volin, K.J.

Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

Grain Boundary Engineering of Lithium-Ion-Conducting Lithium Lanthanum Titanate for Lithium-Air Batteries

DTIC Science & Technology

2015-01-01

Tojo T, Sakurai Y. Synthesis and lithium - ion conductivity for perovskite-type Li3/8Sr7/16Ta3/4Zr1/4O3 solid electrolyte by powder-bed sintering...battery performance is limited by the electrolytic membrane, which needs high Li-ionic conductivity. Lithium lanthanum titanate (Li3xLa(2/3)-xTiO3, or...of the A-site ions and lithium ion conductivity in the perovskite solid solution La0.67-xLi3xTiO3 (x=0.11). Journal of Solid State Ionics. 1999;121

A new anisotropic mesh adaptation method based upon hierarchical a posteriori error estimates

NASA Astrophysics Data System (ADS)

Huang, Weizhang; Kamenski, Lennard; Lang, Jens

2010-03-01

A new anisotropic mesh adaptation strategy for finite element solution of elliptic differential equations is presented. It generates anisotropic adaptive meshes as quasi-uniform ones in some metric space, with the metric tensor being computed based on hierarchical a posteriori error estimates. A global hierarchical error estimate is employed in this study to obtain reliable directional information of the solution. Instead of solving the global error problem exactly, which is costly in general, we solve it iteratively using the symmetric Gauß-Seidel method. Numerical results show that a few GS iterations are sufficient for obtaining a reasonably good approximation to the error for use in anisotropic mesh adaptation. The new method is compared with several strategies using local error estimators or recovered Hessians. Numerical results are presented for a selection of test examples and a mathematical model for heat conduction in a thermal battery with large orthotropic jumps in the material coefficients.

Anisotropic rheology of a polycrystalline aggregate and convection in planetary mantles

NASA Astrophysics Data System (ADS)

Pouilloux, L. S.; Labrosse, S.; Kaminski, E.

2011-12-01

Observations of seismic anisotropy in the Earth mantle is often related to the crystal preferred orientation of polycrystalline aggregates. In this case, the physical properties depends on the direction and require the use of tensors to be fully described. In particular, the viscosity must be defined as a fourth order tensor whereas the thermal conductivity is a 2nd order tensor. However, the dynamical implications of such physical properties have received little attention until now. In this work, we present the mathematical formulation for an anisotropic medium and the relationship with dislocation creep deformation. We explore extensively the problem of the onset of Rayleigh-Bénard convection with such anisotropic properties. We finally presents some numerical results on the time-dependent problem using an orthotropic law for an ice polycrystal. Geophysical implications of this work related to the dynamics of planetary mantles are discussed, especially the potential of anisotropic rheology to localize deformation.

Anisotropic in-Plane Thermal Conductivity Observed in Few-Layer Black Phosphorus

DTIC Science & Technology

2015-10-16

optoelectronic devices where the anisotropic properties might be used10,21–23. Although electronic and photovoltaic properties have been extensively...investigated, thermal transport studies of BP, especially experimental ones, are still lacking. Recently, the thermoelectric power of bulk BP has been...reported, indicating that BP could be used as an efficient thermoelectric material at around 380K24. Some recent first-principles studies also raised

Characterization of Thallium Bromide (TlBr) for Room Temperature Radiation Detectors

NASA Astrophysics Data System (ADS)

Smith, Holland McTyeire

Thallium bromide (TlBr) has emerged as a remarkably well-suited material for room temperature radiation detection. The unique combination of high-Z elements, high density, suitable band gap, and excellent electrical transport properties present in TlBr have brought device performance up to par with CdZnTe (CZT), the current market-leading room temperature radiation detector material. TlBr research is at an earlier stage than that of CZT, giving hope that the material will see even further improvement in electronic properties. Improving a resistive semiconductor material requires knowledge of deep levels present in the material and the effects of these deep levels on transport properties. Very few deep level studies have been conducted on TlBr, and none with the depth required to generate useful growth suggestions. In this dissertation, deep levels in nominally undoped and doped TlBr samples are studied with electrical and optical methods. Photo-Induced Conductivity Transient Spectroscopy (PICTS) is used to discover many deep levels in TlBr electrically. These levels are compared to sub-band gap optical transitions originating from defects observed in emission spectra. The results of this research indicate that the origin of resistivity in TlBr is likely due to deep level defects pinning the Fermi level at least ˜0.7 eV from either the conduction or valence band edge. The effect of dopants and deep levels on transport in TlBr is assessed with microwave photoconductivity decay analysis. It is found that Pb-, Se-, and O-doping decreases carrier lifetime in TlBr, whereas C-doping does not. TlBr exhibits weak ionic conductivity at room temperature, which both negatively affects the leakage current of detectors and leads to device degradation over time. Researchers are actively looking for ways to reduce or eliminate the ionic conductivity, but are faced with an intriguing challenge of materials engineering: is it possible to mitigate the ionic conduction of TlBr without harming the excellent electronic transport properties? Doping TlBr in order to control the ionic conductivity has been proposed and shown to be effective in reducing dark ionic current, but the electronic effects of the dopants has not been previously studied in detail. In this dissertation, the electronic effects of dopants introduced for ionic reasons are evaluated.

Conductometry of electrolyte solutions

NASA Astrophysics Data System (ADS)

Safonova, Lyubov P.; Kolker, Arkadii M.

1992-09-01

A review is given of the theories of the electrical conductance of electrolyte solutions of different ionic strengths and concentrations, and of the models of ion association. An analysis is made of the methods for mathematical processing of experimental conductometric data. An account is provided of various theories describing the dependence of the limiting value of the ionic electrical conductance on the properties of the solute and solvent. The bibliography includes 115 references.

Synthesis of Long-Chain-Branched (LCB) Polysulfones for Multifunctional Transport Membranes

DTIC Science & Technology

2010-09-01

R.; Dutta, N. K. Interfacial Interactions in Aprotic Ionic Liquid Based Protonic Membrane and Its Correlation with High Temperature Conductivity...rigidity. The series of novel polymers was characterized for chemical structure, thermal transitions, and molecular weight. Ionic conductivity was tested...Although much progress exists based on perfluorosulfonated platforms ( Nafion , σ ≈ 10-1 – 10-2 S/cm) new and more complicated parameters arise as

Ionic Conductivity, Structural Deformation and Programmable Anisotropy of DNA Origami in Electric Field

PubMed Central

Li, Chen-Yu; Hemmig, Elisa A.; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia

2015-01-01

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules—a DNA origami plate— placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg2+ ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA. PMID:25623807

Ionic conductivity, structural deformation, and programmable anisotropy of DNA origami in electric field.

PubMed

Li, Chen-Yu; Hemmig, Elisa A; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia; Keyser, Ulrich F; Aksimentiev, Aleksei

2015-02-24

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules, a DNA origami plate, placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg(2+) ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA.

Sound attenuation and absorption by anisotropic fibrous materials: Theoretical and experimental study

NASA Astrophysics Data System (ADS)

Bravo, Teresa; Maury, Cédric

2018-03-01

This paper describes analytical and experimental studies carried out to examine the attenuation and absorption properties of rigidly-backed fibrous anisotropic materials in contact with a uniform mean flow. The aim is to provide insights for the development of non-locally reacting wall-treatments able to dissipate the noise induced by acoustic excitations over in-duct or external lining systems. A model of sound propagation in anisotropic bulk-reacting liners is presented that fully accounts for anisotropic losses due to heat conduction, viscous dissipation and diffusion processes along and across the material fibres as well as for the convective effect of an external flow. The propagation constant for the least attenuated mode of the coupled system is obtained using a simulated annealing search method. The predicted acoustical performance is validated in the no-flow case for a wide range of fibre diameters. They are assessed against impedance tube and free-field pressure-velocity measurements of the normal incidence absorption coefficient and surface impedance. Parametric studies are then conducted to determine the key constitutive parameters such as the fibres orientation or the amount of anisotropy that mostly influence the axial attenuation or the normal absorption. They are supported by a low-frequency approximation to the axial attenuation under a low-speed flow.

Large anisotropic thermoelectricity in perovskite related layered structure: SrnNbnO3n+2 (n=4,5)

NASA Astrophysics Data System (ADS)

Sakai, Akihiro; Kanno, Tsutomu; Takahashi, Kouhei; Yamada, Yuka; Adachi, Hideaki

2010-11-01

We measured the thermal and charge transport properties of perovskite-related layered structures. Strontium-Niobates, which were expressed as SrnNbnO3n+2 (n =4: Sr1.8La0.2Nb2O7, n =5: Sr5Nb5O17), to explore their thermoelectricities and thermal anisotropies. The behaviors of the thermoelectric parameters (thermal conductivity, Seebeck coefficient, resistivity) were strongly anisotropic in all crystallographic axes (a, b, and c) and large anisotropy exists even in the in-plane direction of the layered structure. Especially, along the a-axis in which corner-sharing NbO6 octahedra aligned straightly, contrastive properties were observed between Sr1.8La0.2Nb2O7 and Sr5Nb5O17. For Sr1.8La0.2Nb2O7, a thermally activated charge conduction is pronounced in the temperature dependence of Seebeck coefficient and resistivity, on the other hand, it was a metallic nature for Sr5Nb5O17. In both compounds, ZT results in anisotropic due to the anisotropic properties of thermoelectric parameters, the best performance is commonly observed in the a-axis. The respective ZT values at room temperature are 3.5×10-2 and 3.6×10-3.

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts

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

Tripathy, Satya N., E-mail: satyanarayantripathy@gmail.com; Wojnarowska, Zaneta; Knapik, Justyna

2015-05-14

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10{sup −1}-10{sup 6} Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transitionmore » temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai’s coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.« less

On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

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

Anand, P. B., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in

2014-01-28

Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO)more » (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.« less

Electroosmotic flow and ionic conductance in a pH-regulated rectangular nanochannel

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Sadeghi, Arman

2017-06-01

Infinite series solutions are obtained for electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties of long pH-regulated rectangular nanochannels of low surface potential utilizing the double finite Fourier transform method. Closed form expressions are also obtained for channels of large height to width ratio for which the depthwise variations vanish. Neglecting the Stern layer impact, the effects of EDL (Electric Double Layer) overlap, multiple ionic species, and association/dissociation reactions on the surface are all taken into account. Moreover, finite-element-based numerical simulations are conducted to account for the end effects as well as to validate the analytical solutions. We show that, with the exception of the migratory ionic conductivity, all the physicochemical parameters are strong functions of the channel aspect ratio. Accordingly, a slit geometry is not a good representative of a rectangular channel when the width is comparable to the height. It is also observed that the distribution of the electrical potential is not uniform over the surface of a charge-regulated channel. In addition, unlike ordinary channels for which an increase in the background salt concentration is always accompanied by higher flow rates, quite the opposite may be true for a pH-regulated duct at higher salt concentrations.

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

NASA Astrophysics Data System (ADS)

Subramania, A.; Kalyana Sundaram, N. T.; Sukumar, N.

A micro-porous polymer electrolyte based on PVA was obtained from PVA-PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301-351 K. It is observed that a 2 M LiClO 4 solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10 -3 S cm -1 at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn 2O 4 cell to reveal the compatibility and electrochemical stability between electrode materials.

Variable range hopping electric and thermoelectric transport in anisotropic black phosphorus

DOE PAGES

Liu, Huili; Sung Choe, Hwan; Chen, Yabin; ...

2017-09-05

Black phosphorus (BP) is a layered semiconductor with a high mobility of up to ~1000 cm 2 V -1 s -1 and a narrow bandgap of ~0.3 eV, and shows potential applications in thermoelectrics. In stark contrast to most other layered materials, electrical and thermoelectric properties in the basal plane of BP are highly anisotropic. In order to elucidate the mechanism for such anisotropy, we fabricated BP nanoribbons (~100 nm thick) along the armchair and zigzag directions, and measured the transport properties. It is found that both the electrical conductivity and Seebeck co efficient increase with temperature, a behavior contradictorymore » to that of traditional semiconductors. The three-dimensional variable range hopping model is adopted to analyze this abnormal temperature dependency of electrical conductivity and Seebeck coefficient. Furthermore, the hopping transport of the BP nanoribbons, attributed to high density of trap states in the samples, provides a fundamental understanding of the anisotropic BP for potential thermoelectric applications.« less

Variable range hopping electric and thermoelectric transport in anisotropic black phosphorus

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

Liu, Huili; Sung Choe, Hwan; Chen, Yabin

Black phosphorus (BP) is a layered semiconductor with a high mobility of up to ~1000 cm 2 V -1 s -1 and a narrow bandgap of ~0.3 eV, and shows potential applications in thermoelectrics. In stark contrast to most other layered materials, electrical and thermoelectric properties in the basal plane of BP are highly anisotropic. In order to elucidate the mechanism for such anisotropy, we fabricated BP nanoribbons (~100 nm thick) along the armchair and zigzag directions, and measured the transport properties. It is found that both the electrical conductivity and Seebeck co efficient increase with temperature, a behavior contradictorymore » to that of traditional semiconductors. The three-dimensional variable range hopping model is adopted to analyze this abnormal temperature dependency of electrical conductivity and Seebeck coefficient. Furthermore, the hopping transport of the BP nanoribbons, attributed to high density of trap states in the samples, provides a fundamental understanding of the anisotropic BP for potential thermoelectric applications.« less

An assessment of first-order stochastic dispersion theories in porous media

NASA Astrophysics Data System (ADS)

Chin, David A.

1997-12-01

Random realizations of three-dimensional exponentially correlated hydraulic conductivity fields are used in a finite-difference numerical flow model to calculate the mean and covariance of the corresponding Lagrangian-velocity fields. The dispersivity of the porous medium is then determined from the Lagrangian-velocity statistics using the Taylor definition. This estimation procedure is exact, except for numerical errors, and the results are used to assess the accuracy of various first-order dispersion theories in both isotropic and anisotropic porous media. The results show that the Dagan theory is by far the most robust in both isotropic and anisotropic media, producing accurate values of the principal dispersivity components for σy as high as 1.0, In the case of anisotropic media where the flow is at an angle to the principal axis of hydraulic conductivity, it is shown that the dispersivity tensor is rotated away from the flow direction in the non-Fickian phase, but eventually coincides with the flow direction in the Fickian phase.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

NASA Astrophysics Data System (ADS)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

New Pyrazolium Salts as a Support for Ionic Liquid Crystals and Ionic Conductors

PubMed Central

Pastor, María Jesús; Sánchez, Ignacio; Schmidt, Rainer; Cano, Mercedes

2018-01-01

Ionic liquid crystals (ILCs) are a class of materials that combine the properties of liquid crystals (LCs) and ionic liquids (ILs). This type of materials is directed towards properties such as conductivity in ordered systems at different temperatures. In this work, we synthesize five new families of ILCs containing symmetrical and unsymmetrical substituted pyrazolium cations, with different alkyl long-chains, and anions such as Cl−, BF4−, ReO4−, p-CH3-6H4SO3− (PTS) and CF3SO3− (OTf). We study their thermal behavior by polarized light optical microscopy (POM) and differential scanning calorimetry (DSC). All of them, except those with OTf as counteranion, show thermotropic mesomorphism. The observations by POM reveal textures of lamellar mesophases. Those agree with the arrangement observed in the X-ray crystal structure of [H2pzR(4),R(4)][ReO4]. The nature of the mesophases is also confirmed by variable temperature powder X-ray diffraction. On the other hand, the study of the dielectric properties at variable temperature in mesomorphic (Cl− and BF4−) and non-mesomorphic (OTf) salts indicates that the supramolecular arrangement of the mesophase favors a greater ionic mobility and therefore ionic conductivity. PMID:29614030

Dynamical anisotropic response of black phosphorus under magnetic field

NASA Astrophysics Data System (ADS)

Liu, Xuefeng; Lu, Wei; Zhou, Xiaoying; Zhou, Yang; Zhang, Chenglong; Lai, Jiawei; Ge, Shaofeng; Sekhar, M. Chandra; Jia, Shuang; Chang, Kai; Sun, Dong

2018-04-01

Black phosphorus (BP) has emerged as a promising material candidate for next generation electronic and optoelectronic devices due to its high mobility, tunable band gap and highly anisotropic properties. In this work, polarization resolved ultrafast mid-infrared transient reflection spectroscopy measurements are performed to study the dynamical anisotropic optical properties of BP under magnetic fields up to 9 T. The relaxation dynamics of photoexcited carrier is found to be insensitive to the applied magnetic field due to the broadening of the Landau levels and large effective mass of carriers. While the anisotropic optical response of BP decreases with increasing magnetic field, its enhancement due to the excitation of hot carriers is similar to that without magnetic field. These experimental results can be well interpreted by the magneto-optical conductivity of the Landau levels of BP thin film, based on an effective k · p Hamiltonian and linear response theory. These findings suggest attractive possibilities of multi-dimensional control of anisotropic response (AR) of BP with light, electric and magnetic field, which further introduces BP to the fantastic magnetic field sensitive applications.

Anisotropic thermal transport in van der Waals layered alloys WSe2(1-x)Te2x

NASA Astrophysics Data System (ADS)

Qian, Xin; Jiang, Puqing; Yu, Peng; Gu, Xiaokun; Liu, Zheng; Yang, Ronggui

2018-06-01

Transition metal dichalcogenide (TMD) alloys have attracted great interest in recent years due to their tunable electronic properties and the semiconductor-metal phase transition along with their potential applications in solid-state memories and thermoelectrics among others. However, the thermal conductivity of layered TMD alloys remains largely unexplored despite that it plays a critical role in the reliability and functionality of TMD-enabled devices. In this work, we study the composition- and temperature-dependent anisotropic thermal conductivity of the van der Waals layered TMD alloys WSe2(1-x)Te2x in both the in-plane direction (parallel to the basal planes) and the cross-plane direction (along the c-axis) using time-domain thermoreflectance measurements. In the WSe2(1-x)Te2x alloys, the cross-plane thermal conductivity is observed to be dependent on the heating frequency (modulation frequency of the pump laser) due to the non-equilibrium transport between different phonon modes. Using a two-channel heat conduction model, we extracted the anisotropic thermal conductivity at the equilibrium limit. A clear discontinuity in both the cross-plane and the in-plane thermal conductivity is observed as x increases from 0.4 to 0.6 due to the phase transition from the 2H to the Td phase in the layered alloys. The temperature dependence of thermal conductivity for the TMD alloys was found to become weaker compared with the pristine 2H WSe2 and Td WTe2 due to the atomic disorder. This work serves as an important starting point for exploring phonon transport in layered alloys.

Ballistic anisotropic magnetoresistance in core-shell nanowires and rolled-up nanotubes

NASA Astrophysics Data System (ADS)

Chang, Ching-Hao; Ortix, Carmine

2017-01-01

In ferromagnetic nanostructures, the ballistic anisotropic magnetoresistance (BAMR) is a change in the ballistic conductance with the direction of magnetization due to spin-orbit interaction. Very recently, a directional dependent ballistic conductance has been predicted to occur in a number of newly synthesized nonmagnetic semiconducting nanostructures subject to externally applied magnetic fields, without necessitating spin-orbit coupling. In this paper, we review past works on the prediction of this BAMR effect in core-shell nanowires (CSN) and rolled-up nanotubes (RUNTs). This is complemented by new results, we establish for the transport properties of tubular nanosystems subject to external magnetic fields.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

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

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

Geometry effect on electrokinetic flow and ionic conductance in pH-regulated nanochannels

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Moosavi, Ali; Sadeghi, Arman

2017-12-01

Semi-analytical solutions are obtained for the electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties associated with long pH-regulated nanochannels of arbitrary but constant cross-sectional area. The effects of electric double layer overlap, multiple ionic species, and surface association/dissociation reactions are all taken into account, assuming low surface potentials. The method of analysis includes series solutions which the pertinent coefficients are obtained by applying the wall boundary conditions using either of the least-squares or point matching techniques. Although the procedure is general enough to be applied to almost any arbitrary cross section, nine nanogeometries including polygonal, trapezoidal, double-trapezoidal, rectangular, elliptical, semi-elliptical, isosceles triangular, rhombic, and isotropically etched profiles are selected for presentation. For the special case of an elliptic cross section, full analytical solutions are also obtained utilizing the Mathieu functions. We show that the geometrical configuration plays a key role in determination of the ionic conductance, surface charge density, electrical potential and velocity fields, and proton enhancement. In this respect, the net electric charge and convective ionic conductance are higher for channels of larger perimeter to area ratio, whereas the opposite is true for the average surface charge density and mean velocity; the geometry impact on the two latest ones, however, vanishes if the background salt concentration is high enough. Moreover, we demonstrate that considering a constant surface potential equal to the average charge-regulated potential provides sufficiently accurate results for smooth geometries such as an ellipse at medium-high aspect ratios but leads to significant errors for geometries having narrow corners such as a triangle.

Interplay of Transport and Morphology in Nanostructured Ion-Containing Polymers

NASA Astrophysics Data System (ADS)

Park, Moon Jeong

The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community to develop innovative ways to improve energy storage and find more efficient methods of transporting the energy. Polymers containing charged species that show high ionic conductivity and good mechanical integrity are the essential components of these energy storage and transport systems. In this talk, first, I will present a fundamental understanding of the thermodynamics and transport in ion-containing block copolymers with a focus on the structure-property relationships. Tailoring the intermolecular interactions between the polymer matrix and the embedded charges appeared to be vital for controlling the transport properties. Particularly, the achievement of well-defined self-assembled morphologies with three-dimensional symmetries has proven to facilitate fast ion transport by constructing less tortuous ion-conducting pathways. Examples of attained morphologies include disorder, lamellae, gyroid, Fddd, hexagonal cylinder, body-centered cubic, face-centered cubic, and A15 phases. Second, various strategies for accessing high cation transference number as well as improved ionic conductivity from ionic-containing polymers are enclosed; (1) the inclusion of terminal ionic units as a new means to control the nanoscale morphologies and the transport efficiency of block copolymer electrolytes and (2) the addition of zwitterions that offered a polar medium close to water, and accordingly increased the charge density and ionic conductivity. The obtained knowledge on polymer electrolytes could be used in a wide range of emerging nanotechnologies such as fuel cells, lithium batteries, and electro-active actuators.

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

Supramolecular ionogel lubricants with imidazolium-based ionic liquids bearing the urea group as gelator.

PubMed

Yu, Qiangliang; Wu, Yang; Li, DongMei; Cai, Meirong; Zhou, Feng; Liu, Weimin

2017-02-01

A new class of ionic liquid gels (ionogels) is prepared through the supramolecular self-assembly of imidazolium-based ionic liquids (ILs) bearing the urea group as gelators in normal ILs. The ILs gelator can self-assemble through hydrogen bonding and hydrophobic interaction to form analogous lamellar structures and solidify base ILs. The obtained ionogels exhibit superior anticorrosion and conductivity characteristics. Moreover, ionogels show fully thermoreversible and favorable thixotropic characteristics, such that they can be used as high-performance semisolid conductive lubricants. The tribological tests reveal that these ionogels lubricants can effectively reduce the friction of sliding pairs effectively and have better tribological performance than the pure ILs under harsh conditions. Ionogel lubricants not only maintain the excellent tribological properties and conductivity of ILs, but also prevent base liquids from creeping and leakage. Therefore, ionogel lubricants can be potentially used in the conductive parts of electrical equipments. Copyright © 2016 Elsevier Inc. All rights reserved.

Large apparent electric size of solid-state nanopores due to spatially extended surface conduction.

PubMed

Lee, Choongyeop; Joly, Laurent; Siria, Alessandro; Biance, Anne-Laure; Fulcrand, Rémy; Bocquet, Lydéric

2012-08-08

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

Non-crosslinked, amorphous, block copolymer electrolyte for batteries

DOEpatents

Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

2006-04-11

Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

Deformation modeling and constitutive modeling for anisotropic superalloys

NASA Technical Reports Server (NTRS)

Milligan, Walter W.; Antolovich, Stephen D.

1989-01-01

A study of deformation mechanisms in the single crystal superalloy PWA 1480 was conducted. Monotonic and cyclic tests were conducted from 20 to 1093 C. Both (001) and near-(123) crystals were tested, at strain rates of 0.5 and 50 percent/minute. The deformation behavior could be grouped into two temperature regimes: low temperatures, below 760 C; and high temperatures, above 820 to 950 C depending on the strain rate. At low temperatures, the mechanical behavior was very anisotropic. An orientation dependent CRSS, a tension-compression asymmetry, and anisotropic strain hardening were all observed. The material was deformed by planar octahedral slip. The anisotropic properties were correlated with the ease of cube cross-slip, as well as the number of active slip systems. At high temperatures, the material was isotropic, and deformed by homogeneous gamma by-pass. It was found that the temperature dependence of the formation of superlattice-intrinsic stacking faults was responsible for the local minimum in the CRSS of this alloy at 400 C. It was proposed that the cube cross-slip process must be reversible. This was used to explain the reversible tension-compression asymmetry, and was used to study models of cross-slip. As a result, the cross-slip model proposed by Paidar, Pope and Vitek was found to be consistent with the proposed slip reversibility. The results were related to anisotropic viscoplastic constitutive models. The model proposed by Walter and Jordan was found to be capable of modeling all aspects of the material anisotropy. Temperature and strain rate boundaries for the model were proposed, and guidelines for numerical experiments were proposed.

Investigation of bio polymer electrolyte based on cellulose acetate-ammonium nitrate for potential use in electrochemical devices.

PubMed

Monisha, S; Mathavan, T; Selvasekarapandian, S; Milton Franklin Benial, A; Aristatil, G; Mani, N; Premalatha, M; Vinoth Pandi, D

2017-02-10

Proton conducting materials create prime interest in electro chemical device development. Present work has been carried out to design environment friendly new biopolymer electrolytes (BPEs) using cellulose acetate (CA) complex with different concentrations of ammonium nitrate (NH 4 NO 3 ), which have been prepared as film and characterized. The 50mol% CA and 50mol% NH 4 NO 3 complex has highest ionic conductivity (1.02×10 -3 Scm -1 ). Differential scanning calorimetry shows the changes in glass transition temperature depends on salt concentration. Structural analysis indicates that the highest ionic conductivity complex exhibits more amorphous nature. Vibrational analysis confirms the complex formation, which has been validated theoretically by Gaussian 09 software. Conducting element in the BPEs has been predicted. Primary proton battery and proton exchange membrane fuel cell have been developed for highest ionic conductivity complex. Output voltage and power performance has been compared for single fuel cell application, which manifests the present BPE holds promise application in electrochemical devices. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of pressure on decoupling of ionic conductivity from structural relaxation in hydrated protic ionic liquid, lidocaine HCl.

PubMed

Swiety-Pospiech, A; Wojnarowska, Z; Hensel-Bielowka, S; Pionteck, J; Paluch, M

2013-05-28

Broadband dielectric spectroscopy and pressure-temperature-volume methods are employed to investigate the effect of hydrostatic pressure on the conductivity relaxation time (τσ), both in the supercooled and glassy states of protic ionic liquid lidocaine hydrochloride monohydrate. Due to the decoupling between the ion conductivity and structural dynamics, the characteristic change in behavior of τσ(T) dependence, i.e., from Vogel-Fulcher-Tammann-like to Arrhenius-like behavior, is observed. This crossover is a manifestation of the liquid-glass transition of lidocaine HCl. The similar pattern of behavior was also found for pressure dependent isothermal measurements. However, in this case the transition from one simple volume activated law to another was noticed. Additionally, by analyzing the changes of conductivity relaxation times during isothermal densification of the sample, it was found that compression enhances the decoupling of electrical conductivity from the structural relaxation. Herein, we propose a new parameter, dlogRτ∕dP, to quantify the pressure sensitivity of the decoupling phenomenon. Finally, the temperature and volume dependence of τσ is discussed in terms of thermodynamic scaling concept.

Anionic membrane and ionomer based on poly(2,6-dimethyl-1,4-phenylene oxide) for alkaline membrane fuel cells

NASA Astrophysics Data System (ADS)

Ong, Ai Lien; Saad, Saeed; Lan, Rong; Goodfellow, Robert J.; Tao, Shanwen

2011-10-01

Hydroxyl-ion conductive poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membranes with different characteristics were prepared via relatively simple bromination/amination serial reactions with reduced number of involved chemicals and shorter reaction time. The effects of reactants ratio, reaction atmosphere, polymer concentration, casting solvent, and hydroxylation treatment on reaction were investigated in details. The microstructure, water uptake, swelling ratio, ion-exchange capacity and ionic conductivity of the membranes were also studied. The obtained results demonstrate that, the ionic conductivity of the membrane is dependent on casting solvent. The N-methyl-2-pyrrolidonecast membrane exhibits the highest conductivity with the thinnest film. Although the membrane was prepared via a relatively simple preparation route with least toxic chemicals, a competitive ionic conductivity value of 1.64 × 10-2 S cm-1 was achieved at 60 °C. A power density of 19.5 mW cm-2 has been demonstrated from the alkaline membrane fuel cell operated at 70 °C, assembled from the entirely homemade membrane electrode assembly without any hot-pressing.

MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

PubMed

Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

2013-03-21

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Predicting Carbonate Species Ionic Conductivity in Alkaline Anion Exchange Membranes

DTIC Science & Technology

2012-06-01

This method has been used previously with both PEM and AEM fuel cells and demonstrated its ability to accurately predict ionic conductivity [2,9,24...water. In an AMFC, the mobile species is a hydroxide ion (OH - ) and in a PEM fuel cell , the proton is solvated with a water molecule forming...membrane synthesis techniques have produced polymer electrolyte membranes that are capable of transporting anions in alkaline membrane fuel cells

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

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia

Fast ion transport channels at interfaces in thin films have attracted great attention due to a range of potential applications for energy materials and devices, for, solid oxide fuel cells, sensors, and memories. Here, it is shown that in vertical nanocomposite heteroepitaxial films of SrZrO 3–RE 2O 3 (RE = Sm, Eu, Gd, Dy, and Er) the ionic conductivity of the composite can be tuned and strongly enhanced using embedded, stiff, and vertical nanopillars of RE 2O 3. With increasing lattice constant of RE 2O 3 from Er 2O 3 to Sm 2O 3, it is found that the tensilemore » strain in the SrZrO 3 increases proportionately, and the ionic conductivity of the composite increases accordingly, by an order of magnitude. Lastly, the results here conclusively show, for the first time, that strain in films can be effectively used to tune the ionic conductivity of the materials.« less

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

The Electrolyte Factor in O2 Reduction Electrocatalysis

DTIC Science & Technology

1993-04-23

molecule thick and does not seem to interfere with 02 and water/proton transport at this interface. This layer resembles a self-ordered Langmuir - Blodgett ... liquid electrolyte from within the polymer is in contact with the catalyst and completes the ionic circuit between the ionic conducting polymer and the...the free energy of adsorption of H2 0 and ionic components because of the lower effective dielectric constant in the electrolyte phase immediately

Electrical conductivity anomaly beneath Mare Serenitatis detected by Lunokhod 2 and Apollo 16 magnetometers

NASA Technical Reports Server (NTRS)

Vanian, L. L.; Vnuchkova, T. A.; Egorov, I. V.; Basilevskii, A. T.; Eroshenko, E. G.; Fainberg, E. B.; Dyal, P.; Daily, W. D.

1979-01-01

Magnetic fluctuations measured by the Lunokhod 2 magnetometer in the Bay Le Monnier are distinctly anisotropic when compared to simultaneous Apollo 16 magnetometer data measured 1100 km away in the Descartes highlands. This anisotropy can be explained by an anomalous electrical conductivity of the upper mantle beneath Mare Serenitatis. A model is presented of anomalously lower electrical conductivity beneath Serenitatis and the simultaneous magnetic data from the Lunokhod 2 site at the mare edge and the Apollo 16 site are compared to the numerically calculated model solutions. This comparison indicates that the anisotropic fluctuations can be modeled by a nonconducting layer in the lunar lithosphere which is 150 km thick beneath the highlands and 300 km thick beneath Mare Serenitatis. A decreased electrical conductivity in the upper mantle beneath the mare may be due to a lower temperature resulting from heat carried out the magma source regions to the surface during mare flooding.

Dynamic mechanism of equivalent conductivity minimum of electrolyte solution

NASA Astrophysics Data System (ADS)

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

2011-10-01

The theory on electric conductivity of electrolyte solutions we have developed [T. Yamaguchi, T. Matsuoka, and S. Koda, J. Chem. Phys. 127, 064508 (2007)] is applied to a model electrolyte solution that shows a minimum of equivalent conductivity as the function of concentration [T. Yamaguchi, T. Akatsuka, and S. Koda, J. Chem. Phys. 134, 244506 (2011)]. The theory succeeds in reproducing the equivalent conductivity minimum, whereas the mode-coupling theory (MCT) underestimates the conductivity in the low-concentration regime. The theory can also reproduce the decrease in the relaxation time of conductivity with increasing the concentration we have demonstrated with a Brownian dynamics simulation. A detailed analysis shows that the relaxation of the conductivity occurs through two processes. The faster one corresponds to the collision between a cation and an anion, and the slower one does to the polarization of the ionic atmosphere. The increase in the equivalent conductivity with concentration is attributed to the decrease in the effect of the ionic atmosphere, which is in turn explained by the fact that the counter ion cannot penetrate into the repulsive core when the Debye screening length is compatible or smaller than the ionic diameter. The same mechanism is also observed in MCT calculation with static structure factor determined by mean-spherical approximation.

Ionomers for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph

For ionic actuators and battery separators, it is vital to utilize single-ion conducting ionomers that avoid the detrimental polarization of other ions. Single-ion conducting ionomers are synthesized based on DFT calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for battery separators that conduct Li+ or Na+. Characterization by X-ray scattering, dielectric spectroscopy, FTIR, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. 7Li NMR diffusion measurements find that diffusion is faster than expected by conductivity using the Nernst-Einstein equation, which means that the majority of Li diffusion occurs by ion pairs moving with the polymer segmental motion. Segmental motion only contributes to ionic conduction in the rare event that one of these ion pairs has an extra Li (a positive triple ion). This leads us to a new metric for ion-conducting soft materials, the product of the cation number density p0 and their diffusion coefficient D; p0D is the diffusive flux of lithium ions. This new metric has a maximum at intermediate ion content that corresponds to the overlap of ion pair polarizability volumes. At higher ion contents, the ion pairs interact strongly and form larger aggregation states that retard segmental motion of both mobile ion pairs and triple ions.

First-Principles Characterization of the Unknown Crystal Structure and Ionic Conductivity of Li7P2S8I as a Solid Electrolyte for High-Voltage Li Ion Batteries.

PubMed

Kang, Joonhee; Han, Byungchan

2016-07-21

Using first-principles density functional theory calculations and ab initio molecular dynamics (AIMD) simulations, we demonstrate the crystal structure of the Li7P2S8I (LPSI) and Li ionic conductivity at room temperature with its atomic-level mechanism. By successively applying three rigorous conceptual approaches, we identify that the LPSI has a similar symmetry class as Li10GeP2S12 (LGPS) material and estimate the Li ionic conductivity to be 0.3 mS cm(-1) with an activation energy of 0.20 eV, similar to the experimental value of 0.63 mS cm(-1). Iodine ions provide an additional path for Li ion diffusion, but a strong Li-I attractive interaction degrades the Li ionic transport. Calculated density of states (DOS) for LPSI indicate that electrochemical instability can be substantially improved by incorporating iodine at the Li metallic anode via forming a LiI compound. Our methods propose the computational design concept for a sulfide-based solid electrolyte with heteroatom doping for high-voltage Li ion batteries.

Synthesis of ionic liquids

DOEpatents

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

2008-09-09

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

Synthesis of ionic liquids

DOEpatents

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

2011-11-01

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

Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

NASA Astrophysics Data System (ADS)

Oh, Hyukkeun

Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium-ion batteries was incorporated into a battery cell as a solvent mixture with propylene carbonate and lithium bis(trifluoromethane)sulfonimide impregnated in a free-standing hybrid electrolyte film. Outstanding ionic conductivity was achieved and the lithium half cell comprising a LTO cathode and a lithium metal anode separated by the solid polymer electrolyte showed good cyclability at room temperature and even at 0°C. The presence of a sufficient amount of propylene carbonate, which resulted in flammability of the polymer electrolyte, was discovered to be critical in the electrochemical stability of the polymer electrolyte.

STUDY ON LITHIUM FAST ION CONDUCTORS OF Li2O SiO2 V2O5 SYSTEM

NASA Astrophysics Data System (ADS)

Huang, Geng; Wang, Wenji

Fast ion conductors of Li2O SiO2 V2O5 system have been prepared by using Li2O, SiO2 and V2O5 as starting materials. The optimal ratio of starting materials was designed by Uniform Design. The conductivities of both electric and ionic were investigated. The highest ion conductivity is 1.5 × 10-4S/cm at ambient temperature for the above lithium fast ion conductor system, the electronic conductivity is 4 orders of magnitude lower than the ionic conductivity.

Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

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

Harun, Fatin; Chan, Chin Han; Winie, Tan

Effect of epoxide content on the thermal and conductivity properties of epoxidized natural rubber (ENR) solid polymer nanocomposite electrolytes was investigated. Commercial available epoxidized natural rubber having 25 (ENR25) and 50 mole% (ENR50) epoxide, respectively were incorporated with lithium perchlorate (LiClO{sub 4}) salt and titanium dioxide (TiO{sub 2}) nanofiller via solution casting method. The solid polymer nanocomposite electrolytes were characterized by differential scanning calorimetry (DSC) and impedance spectroscopy (IS) for their thermal properties and conductivity, respectively. It was evident that introduction of LiClO{sub 4} causes a greater increase in glass transition temperature (T{sub g}) and ionic conductivity of ENR50 asmore » compared to ENR25. Upon addition of TiO{sub 2} in ENR/LiClO{sub 4} system, a remarkable T{sub g} elevation was observed for both ENRs where ENR50 reveals a more pronounced changes. It is interesting to note that they exhibit different phenomenon in ionic conductivity with TiO{sub 2} loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.« less

Ionic conductivity measurement in magnesium aluminate spinel and solid state galvanic cell with magnesium aluminate electrolyte

NASA Astrophysics Data System (ADS)

Lee, Myongjai

This thesis work is about the experimental measurement of electronic and ionic conductivities in the MgAl2O4 spinel at 500˜600°C range and exploring the fundamental origin of solid-state galvanic cell behavior in the cell of Al|MgAl2O4|Mg, Al|MgAl2O 4|C, and Mg|MgAl2O4|C, in which at least one metal electrode in common with the composition of the electrolyte. For the electronic conductivity measurement, we have used the ion-blocking Gold and Carbon electrodes which are inert with both Mg and Al ions to suppress the ionic conduction from the total conduction. DC polarization method was used to measure the conduction through Au|MgAl2O4|Au and C|MgAl2O4|C specimens. The measured electrical conductivity using Au|MgAl2O4|Au and C|MgAl2O4|C specimens showed 10-9.3 ˜ 10-8.4 (O·cm) -1 at 600˜720°C range following the Arrhenius-type relation. These conductivity data are in agreement with reported data obtained from Pt and Ag ion-blocking electrodes deposited on MgAl2O4 specimens. For the ionic conductivity measurement, we have used the non-blocking Al and Mg electrodes for Al and Mg ionic conductivities, respectively. Ionic conductivity measurement of Al and Mg in separate manner has not been reported yet. In both Al|MgAl2O4|Al and Mg|MgAl2O 4|Mg specimens, gradual increase of conduction was observed once at the initial period before it reaches the steady state conduction. By DC method on the range of 580˜650°C, steady state Al ionic conductivity was measured from Al|MgAl2O4|Al specimen showing 10 -7.7 ˜ 10-6.8 (O·cm)-1 with the activation energy of 1.9eV in sigma = sigma0 exp-QRT formula. There was no difference in the conductivity by the change of the atmosphere from 5%H2 + 95%N2 mixed gas to pure Ar gas. So it was confirmed that the oxygen defect chemistry did not play a role. For Mg ionic conductivity Mg|MgAl2O4|Mg specimen was used and the measured conductivity shows 10-6.7 ˜ 10-4.4 (O·cm)-1 at 400˜550°C with the activation energy of 1.44eV at Ar gas atmosphere. Higher conductivity of Mg cation than Al cation is in agreement with self-diffusion data reported in the literatures. It's also in agreement with the higher Mg ionic mobility concluded by the formation of MgO layer at the cathode as the result of reaction between Mg ions migration and surrounding oxygen decomposed by the applied voltage. To explore the fundamental origin of the emf in the Mg|MgAl2O 4|Al galvanic cell, we set-up two postulations which are able to explain by the transportation mechanism in the MgAl2O4 with the presence of two cations in the system. The possible mechanisms are (1) Only Mg ion is involved in transportation through the MgAl2O4. Thus the emf is generated from the difference in the activity of Mg between the two electrodes. (2) Both Mg2+ and Al3+ ions are participating in transportation through the MgAl2O 4. In this case, the emf is generated from the difference in the reduction-oxidation potential between Mg and Al. Based on the result that both Al|MgAl2O4|C and Mg|MgAl2O4|C have the emf with C positive polarity, the second suggested mechanism results in the spontaneous composition change inside MgAl2O4 in the both directions of Mg-rich and Al-rich according the electrode materials with fixed C electrode on the other side. Considering the spontaneous reaction involving the composition change of MgAl2O4 to lower free energy of the system, suggested mechanism one is more plausible. In order to confirm that origin of the emf is determined by the activity difference on electrodes, emf measurements were carried out using different Mg activities available by using Mg-Al alloy. OCV was dependent on the difference in the Mg activity on the electrodes of Mg|MgAl2O4|Mg-Al alloy. This result supports the emf is generated by the difference in the activity of Mg ions at the both electrodes.

All-d-Enantiomer of β-Amyloid Peptide Forms Ion Channels in Lipid Bilayers

PubMed Central

2012-01-01

Alzheimer’s disease (AD) is the most common type of senile dementia in aging populations. Amyloid β (Aβ)-mediated dysregulation of ionic homeostasis is the prevailing underlying mechanism leading to synaptic degeneration and neuronal death. Aβ-dependent ionic dysregulation most likely occurs either directly via unregulated ionic transport through the membrane or indirectly via Aβ binding to cell membrane receptors and subsequent opening of existing ion channels or transporters. Receptor binding is expected to involve a high degree of stereospecificity. Here, we investigated whether an Aβ peptide enantiomer, whose entire sequence consists of d-amino acids, can form ion-conducting channels; these channels can directly mediate Aβ effects even in the absence of receptor–peptide interactions. Using complementary approaches of planar lipid bilayer (PLB) electrophysiological recordings and molecular dynamics (MD) simulations, we show that the d-Aβ isomer exhibits ion conductance behavior in the bilayer indistinguishable from that described earlier for the l-Aβ isomer. The d isomer forms channel-like pores with heterogeneous ionic conductance similar to the l-Aβ isomer channels, and the d-isomer channel conductance is blocked by Zn2+, a known blocker of l-Aβ isomer channels. MD simulations further verify formation of β-barrel-like Aβ channels with d- and l-isomers, illustrating that both d- and l-Aβ barrels can conduct cations. The calculated values of the single-channel conductance are approximately in the range of the experimental values. These findings are in agreement with amyloids forming Ca2+ leaking, unregulated channels in AD, and suggest that Aβ toxicity is mediated through a receptor-independent, nonstereoselective mechanism. PMID:22423218

Conductivity percolation in loosely compacted microcrystalline cellulose: An in situ study by dielectric spectroscopy during densification.

PubMed

Nilsson, Martin; Frenning, Göran; Gråsjö, Johan; Alderborn, Göran; Strømme, Maria

2006-10-19

The present study aims at contributing to a complete understanding of the water-induced ionic charge transport in cellulose. The behavior of this transport in loosely compacted microcrystalline cellulose (MCC) powder was investigated as a function of density utilizing a new type of measurement setup, allowing for dielectric spectroscopy measurement in situ during compaction. The ionic conductivity in MCC was found to increase with increasing density until a leveling-out was observed for densities above approximately 0.7 g/cm3. Further, it was shown that the ionic conductivity vs density followed a percolation type behavior signifying the percolation of conductive paths in a 3D conducting network. The density percolation threshold was found to be between approximately 0.2 and 0.4 g/cm3, depending strongly on the cellulose moisture content. The observed percolation behavior was attributed to the forming of interparticulate bonds in the MCC and the percolation threshold dependence on moisture was linked to the moisture dependence of particle rearrangement and plastic deformation in MCC during compaction. The obtained results add to the understanding of the density-dependent water-induced ionic transport in cellulose showing that, at given moisture content, the two major parameters determining the magnitude of the conductivity are the connectedness of the interparticluate bonds and the connectedness of pores with a diameter in the 5-20 nm size range. At densities between approximately 0.7 and 1.2 g/cm3 both the bond and the pore networks have percolated, facilitating charge transport through the MCC compact.

YSZ thin films with minimized grain boundary resistivity

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

Mills, Edmund M.; Kleine-Boymann, Matthias; Janek, Juergen

2016-03-31

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e. g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here we report that the ionic conductivity ofmore » yttria stabilized zirconia thin films with nano-­ columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500°C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film- substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

Heat transfer due to electroconvulsive therapy: Influence of anisotropic thermal and electrical skull conductivity.

PubMed

Menezes de Oliveira, Marilia; Wen, Peng; Ahfock, Tony

2016-09-01

This paper focuses on electroconvulsive therapy (ECT) and head models to investigate temperature profiles arising when anisotropic thermal and electrical conductivities are considered in the skull layer. The aim was to numerically investigate the threshold for which this therapy operates safely to the brain, from the thermal point of view. A six-layer spherical head model consisting of scalp, fat, skull, cerebro-spinal fluid, grey matter and white matter was developed. Later on, a realistic human head model was also implemented. These models were built up using the packages from COMSOL Inc. and Simpleware Ltd. In these models, three of the most common electrode montages used in ECT were applied. Anisotropic conductivities were derived using volume constraint and included in both spherical and realistic head models. The bio-heat transferring problem governed by Laplace equation was solved numerically. The results show that both the tensor eigenvalues of electrical conductivity and the electrode montage affect the maximum temperature, but thermal anisotropy does not have a significant influence. Temperature increases occur mainly in the scalp and fat, and no harm is caused to the brain by the current applied during ECT. The work assures the thermal safety of ECT and also provides a numerical method to investigate other non-invasive therapies. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Scalable explicit implementation of anisotropic diffusion with Runge-Kutta-Legendre super-time stepping

NASA Astrophysics Data System (ADS)

Vaidya, Bhargav; Prasad, Deovrat; Mignone, Andrea; Sharma, Prateek; Rickler, Luca

2017-12-01

An important ingredient in numerical modelling of high temperature magnetized astrophysical plasmas is the anisotropic transport of heat along magnetic field lines from higher to lower temperatures. Magnetohydrodynamics typically involves solving the hyperbolic set of conservation equations along with the induction equation. Incorporating anisotropic thermal conduction requires to also treat parabolic terms arising from the diffusion operator. An explicit treatment of parabolic terms will considerably reduce the simulation time step due to its dependence on the square of the grid resolution (Δx) for stability. Although an implicit scheme relaxes the constraint on stability, it is difficult to distribute efficiently on a parallel architecture. Treating parabolic terms with accelerated super-time-stepping (STS) methods has been discussed in literature, but these methods suffer from poor accuracy (first order in time) and also have difficult-to-choose tuneable stability parameters. In this work, we highlight a second-order (in time) Runge-Kutta-Legendre (RKL) scheme (first described by Meyer, Balsara & Aslam 2012) that is robust, fast and accurate in treating parabolic terms alongside the hyperbolic conversation laws. We demonstrate its superiority over the first-order STS schemes with standard tests and astrophysical applications. We also show that explicit conduction is particularly robust in handling saturated thermal conduction. Parallel scaling of explicit conduction using RKL scheme is demonstrated up to more than 104 processors.

Phase stability and processing of strontium and magnesium doped lanthanum gallate

NASA Astrophysics Data System (ADS)

Zheng, Feng

Fuel Cells are one of the most promising energy transformers with respect to ecological and environmental issues. Solid Oxide Fuel Cells (SOFC) are all solid-state devices. One of the challenges to improve a SOFC is to lower the operating temperature while maintaining or increasing its output voltage. Undoped LaGaO3 is an insulator, doping transforms it into an oxygen-ionic conductor. Sr and Mg doped LaGaO3 (LSGM) perovskite is a new oxygen-ionic conductor with higher conductivity than yttria-stabilized zirconia (YSZ). This material is a candidate for a wide variety of electrochemical devices. In order to realize this potential, the phase stability and processing of this material needs to be investigated in detail. In this study, a systematic investigation of the LSGM materials in terms of phase stability, phase transition, sintering, microstructure and electrical conductivity as functions of temperature, doping content and A/B cation ratio has been carried out. The generalized formula of the materials investigated is (La1--xSrx)A(Ga1--yMg y)BO3--delta. Optimized processing parameters have been obtained by investigating their impact on density change and microstructure. Consequently, a suitable compositional window of the LSGM perovskite has been identified for SOFC electrolyte applications. Based on detailed diffraction analysis, it is found that the undoped LaGaO3 takes on the orthorhombic (Pbnm) symmetry at room temperature. This structure changes to rhombohedral (R3c) at 147 +/- 2°C or changes to monoclinic (I2/a) when the doping level increases from 0.1 to 0.2 moles. We have optimized the compositional window to make the single perovskite phase with high oxygen ionic conductivity (x = 0.10 to 0.20 with A/B ratio between 0.98 to 1.02). The best processing condition, starting from glycine nitrate process (GNP) combustion synthesized ultra-fine LSGM powder, is sintering in air at 1500°C for 2 hours. The doped material has higher oxygen ionic conductivity than YSZ at all temperatures. In addition, based on the structure and phase relations, a high temperature phase diagram for this system has been proposed. Finally, a model has been proposed to account for the high ionic conductivity of this material and to explain the effect of the doping content and the stoichiometry on the ionic conductivity. (Abstract shortened by UMI.)

Structural and superionic properties of Ag+-rich ternary phases within the AgI-MI2 systems

NASA Astrophysics Data System (ADS)

Hull, S.; Keen, D. A.; Berastegui, P.

2002-12-01

The effects of temperature on the crystal structure and ionic conductivity of the compounds Ag2CdI4, Ag2ZnI4 and Ag3SnI5 have been investigated by powder diffraction and impedance spectroscopy techniques. varepsilon-Ag2CdI4 adopts a tetragonal crystal structure under ambient conditions and abrupt increases in the ionic conductivity are observed at 407(2), 447(3) and 532(4) K, consistent with the sequence of transitions varepsilon-Ag2CdI 4 rightarrow beta-Ag2CdI 4 + beta-AgI + CdI2 rightarrow alpha-AgI + CdI2 rightarrow alpha-Ag2CdI4. Hexagonal beta-Ag2CdI4 is metastable at ambient temperature. The ambient-temperature beta phase of Ag2ZnI4 is orthorhombic and the structures of beta-Ag2CdI4 and beta-Ag2ZnI4 can, respectively, be considered as ordered derivatives of the wurtzite (beta) and zincblende (gamma) phases of AgI. On heating Ag2ZnI4, there is a 12-fold increase in ionic conductivity at 481(1) K and a further eightfold increase at 542(3) K. These changes result from decomposition of beta-Ag2ZnI4 into alpha-AgI + ZnI2, followed by the appearance of superionic alpha-Ag2ZnI4 at the higher temperature. The hexagonal crystal structure of alpha-Ag2ZnI4 is a dynamically disordered counterpart to the beta modification. Ag3SnI5 is only stable at temperatures in excess of 370(3) K and possesses a relatively high ionic conductivity (sigma approx 0.19Omega-1 cm-1 at 420 K) due to dynamic disorder of the Ag+ and Sn2+ within a cubic close packed I- sublattice. The implications of these findings for the wider issue of high ionic conductivity in AgI-MI2 compounds is discussed, with reference to recently published studies of Ag4PbI6 and Ag2HgI4 and new data for the temperature dependence of the ionic conductivity of the latter compound.

Capturing the effect of [PF3(C2F5)3]-vs. [PF6]-, flexible anion vs. rigid, and scaled charge vs. unit on the transport properties of [bmim]+-based ionic liquids: a comparative MD study.

PubMed

Kowsari, Mohammad H; Ebrahimi, Soraya

2018-05-16

Comprehensive molecular dynamics simulations are performed to study the average single-particle dynamics and the transport properties of 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [bmim][FAP], ionic liquids (ILs) at 400 K. We applied one of the most widely used nonpolarizable all-atom force fields for ILs, both with the original unit (±1) charges on each ion and with the partial charges uniformly scaled to 80-85%, taking into account the average polarizability and tracing the experimentally compatible transport properties. In all simulations, [bmim]+ was considered to be flexible, while the effect of a flexible vs. rigid structure of the anions and the effect of two applied charge sets on the calculated properties were separately investigated in detail. The simulation results showed that replacing [PF6]- with [FAP]-, considering anion flexibility, and applying the charge-scaled model significantly enhanced the ionic self-diffusion, ionic conductivity, inverse viscosity, and hyper anion preference (HAP). Both of the calculated self-diffusion coefficients from the long-time linear slope of the mean-square displacement (MSD) and from the integration of the velocity autocorrelation function (VACF) for the centers of mass of the ions were used for evaluation of the ionic transference number, HAP, ideal Nernst-Einstein ionic conductivity (σNE), and the Stokes-Einstein viscosity. In addition, for quantification of the degree of complicated ionic association (known as the Nernst-Einstein deviation parameter, Δ) and ionicity phenomena in the two studied ILs, the ionic conductivity was determined more rigorously by the Green-Kubo integral of the electric-current autocorrelation function (ECACF), and then the σGK/σNE ratio was evaluated. It was found that the correlated motion of the (cationanion) neighbors in [bmim][FAP] is smaller than in [bmim][PF6]. The relaxation times of the normalized reorientational autocorrelation functions were computed to gain a deep, molecular-level insight into the rotational motion of the ions. The geometric shape of the ion is a key factor in determining its reorientational dynamics. [bmim]+ shows faster translational and slower rotational dynamics in contrast to [PF6]-.

Characterization of mixed-conducting barium cerate-based perovskites for potential fuel cell applications

NASA Astrophysics Data System (ADS)

Mukundan, R.

Chemical modifications of barium cerium gadolinium oxide through the substitution of Bi, Tb, Pr, Nb and Ta were attempted in an effort to increase the p-type or n-type conductivity, and to develop new mixed-conducting electrodes that are chemically compatible with the Ba(Cesb{1-x}Gdsb{x})Osb{3-x/2} electrolyte. The structure, oxygen non-stoichiometry, electronic and ionic-conductivity of several compositions in the doped-barium cerate systems were studied by X-ray diffraction, TGA, DC and AC conductivity, and EMF measurements. The cathodic overpotential of the mixed (electronic/ionic) conducting compositions in this system, on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte, were also studied using Current Interruption and AC impedance techniques. The substitution of Bi into Ba(Cesb{0.9}Gdsb{0.1})Osb{2.95} lead to a significant increase in the electronic conductivity, and a total conductivity of about 0.94 S/cm was obtained for Ba(Bisb{0.5}Cesb{0.4}Gdsb{0.1})Osb3 at 800sp°C in air. However, the concentration of oxygen-ion vacancies and hence the ionic conductivity decreased due to the oxidation of Bi to the 5sp{+} state. Compositions in the Ba(Bisb{0.5}Cesb{x}Gdsb{0.5-x})Osb3 system also exhibited significant oxygen non-stoichiometry depending upon the ordering of the B-site cations and the relative concentrations of Ce and Gd. However, the absence of any detectable EMF in the non-stoichiometric compositions implied that the oxygen vacancies are strongly associated with the Bisp{3+} cations. Although highly conductive, chemically stable compositions were prepared in the Ba(Bisb{x}Cesb{y}Gdsb{1-(x+y)})Osb{3-d} system, their ionic conductivities were low. The mixed-conduction properties of Ba(Cesb{1-x}Gdsb{x})Osb{3-d} were enhanced under cathode conditions (600-800sp°C in air) by the substitution of Ce by Tb and Pr. While the substitution of Tb resulted in a decrease in the total conductivity, Pr induced a significant increase in the total conductivity at high Pr levels (≥40 mole%) due to an enhancement of the electronic conductivity. The Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9} sample was found to have the best mixed-conducting properties of all the perovskites evaluated, sigmasb{T}=0.75 S/cm in air at 800sp°C, tsb{H+}=0.15 in a wet argon//dry argon gradient, and tsb{0.2-}≈ 0.05 in a dry air//dry argon gradient. The cathodic overpotentials of the mixed-conducting Pr-doped barium cerates were low, and decreased with increasing ionic and electronic conductivity of the electrode. The lowest overpotential was obtained for the Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9}, cathode, and at low current densities was comparable to that of an optimized porous Pt-electrode. While the substitution of Nb and Ta for Ce lead to an enhancement in the electronic conductivity under reducing conditions associated with the increased reduction of Cesp{4+} to Cesp{3+}, the ionic-conductivity of these perovskites was low. There was no evidence for any protonic conductivity in the 15 mole% Nb and Ta substituted barium cerates. Moreover the anodic overpotential and the anode resistance of these perovskites on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte were both high.

Synergistic effects of mixing sulfone and ionic liquid as safe electrolytes for lithium sulfur batteries.

PubMed

Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; Dai, Sheng

2015-01-01

A strategy of mixing both an ionic liquid and sulfone is reported to give synergistic effects of reducing viscosity, increasing ionic conductivity, reducing polysulfide dissolution, and improving safety. The mixtures of ionic liquids and sulfones also show distinctly different physicochemical properties, including thermal properties and crystallization behavior. By using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAh g(-1) (second cycle) by using 40 % 1.0 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide with 60 % 1.0 M LiTFSI in methylisopropylsulfone in the first cycle. This capacity is slightly lower than that obtained in pure 1.0 M LiTFSI as the sulfone electrolyte; however, it exhibits excellent cycling stability and remains as high as 655 mAh g(-1) even after 50 cycles. This strategy provides a method to alleviate polysulfide dissolution and redox shuttle phenomena, at the same time, with improved ionic conductivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and structural characterization of polymer gel electrolytes based on a PEO copolymer and an imidazolium-based ionic liquid for dye-sensitized solar cells.

PubMed

Freitas, Flavio S; de Freitas, Jilian N; Ito, Bruno I; De Paoli, Marco-A; Nogueira, Ana F

2009-12-01

Polymer electrolytes based on mixtures of poly(ethylene oxide-co-propylene oxide) and 1-methyl-3-propyl-imidazolium iodide (MPII) were investigated, aiming at their application in dye-sensitized solar cells (DSSC). The interactions between the copolymer and the ionic liquid were analyzed by infrared spectroscopy and (1)H NMR. The results show interactions between the ether oxygen in the polymer and the hydrogen in the imidazolium cations. The ionic conductivities, electrochemical behaviors, and thermal properties of the electrolytes containing different concentrations of MPII were investigated. The electrolyte containing 70 wt % MPII presented the highest ionic conductivity (2.4 x 10(-3) S cm(-1)) and a diffusion coefficient of 1.9 x 10(-7) cm(2) s(-1). The influence of LiI addition to the electrolytes containing different concentrations of MPII was also investigated. The DSSC assembled with the electrolyte containing 70 wt % MPII showed an efficiency of 3.84% at 100 mW cm(-2). The stability of the devices for a period of 30 days was also evaluated using sealed cells. The devices assembled with the electrolyte containing less ionic liquid showed to be more stable.

A physicochemical investigation of ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc02931c Click here for additional data file.

PubMed Central

Clough, Matthew T.; Crick, Colin R.; Gräsvik, John; Niedermeyer, Heiko; Whitaker, Oliver P.

2015-01-01

Ionic liquids have earned the reputation of being ‘designer solvents’ due to the wide range of accessible properties and the degree of fine-tuning afforded by varying the constituent ions. Mixtures of ionic liquids offer the opportunity for further fine-tuning of properties. A broad selection of common ionic liquid cations and anions are employed to create a sample of binary and reciprocal binary ionic liquid mixtures, which are analysed and described in this paper. Physical properties such as the conductivity, viscosity, density and phase behaviour (glass transition temperatures) are examined. In addition, thermal stabilities of the mixtures are evaluated. The physical properties examined for these formulations are found to generally adhere remarkably closely to ideal mixing laws, with a few consistent exceptions, allowing for the facile prediction and control of properties of ionic liquid mixtures. PMID:29560198

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

PubMed

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

2009-08-01

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

Ionic-liquid materials for the electrochemical challenges of the future

NASA Astrophysics Data System (ADS)

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

2009-08-01

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

Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

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

Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W., E-mail: ed.castner@rutgers.edu

2015-08-14

We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyzemore » the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies.« less

Characterization of anisotropic thermal conductivity of suspended nm-thick black phosphorus with frequency-resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Tianyu; Han, Meng; Wang, Ridong; Yuan, Pengyu; Xu, Shen; Wang, Xinwei

2018-04-01

Frequency-resolved Raman spectroscopy (FR-Raman) is a new technique for nondestructive thermal characterization. Here, we apply this new technique to measure the anisotropic thermal conductivity of suspended nm-thick black phosphorus samples without the need of optical absorption and temperature coefficient. Four samples with thicknesses between 99.8 and 157.6 nm are studied. Based on steady state laser heating and Raman measurement of samples with a specifically designed thermal transport path, the thermal conductivity ratio (κZZ/κAC) is determined to be 1.86-3.06. Based on the FR-Raman measurements, the armchair thermal conductivity is measured as 14-22 W m-1 K-1, while the zigzag thermal conductivity is 40-63 W m-1 K-1. FR-Raman has great potential for studying the thermal properties of various nanomaterials. This study significantly advances our understanding of thermal transport in black phosphorus and facilitates the application of black phosphorus in novel devices.

Entanglement in the Anisotropic Kondo Necklace Model

NASA Astrophysics Data System (ADS)

Mendoza-Arenas, J. J.; Franco, R.; Silva-Valencia, J.

We study the entanglement in the one-dimensional Kondo necklace model with exact diagonalization, calculating the concurrence as a function of the Kondo coupling J and an anisotropy η in the interaction between conduction spins, and we review some results previously obtained in the limiting cases η = 0 and 1. We observe that as J increases, localized and conduction spins get more entangled, while neighboring conduction spins diminish their concurrence; localized spins require a minimum concurrence between conduction spins to be entangled. The anisotropy η diminishes the entanglement for neighboring spins when it increases, driving the system to the Ising limit η = 1 where conduction spins are not entangled. We observe that the concurrence does not give information about the quantum phase transition in the anisotropic Kondo necklace model (between a Kondo singlet and an antiferromagnetic state), but calculating the von Neumann block entropy with the density matrix renormalization group in a chain of 100 sites for the Ising limit indicates that this quantity is useful for locating the quantum critical point.

Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

PubMed

Murthy, Arun; Manthiram, Arumugam

2011-06-28

Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

Iodopropyl-branched polysiloxane gel electrolytes with improved ionic conductivity upon cross-linking.

PubMed

De Gregorio, G L; Giannuzzi, R; Cipolla, M P; Agosta, R; Grisorio, R; Capodilupo, A; Suranna, G P; Gigli, G; Manca, M

2014-11-21

We here report the implementation of poly[(3-N-methylimidazoliumpropyl)methylsiloxane-co-dimethylsiloxane]iodides as suitable polymeric hosts for a novel class of in situ cross-linkable iodine/iodide-based gel-electrolytes for dye-sensitized solar cells. The polymers are first partially quaternized and then subjected to a thermal cross-linking which allows the formation of a 3D polymeric network which is accompanied by a dramatic enhancement of the ionic conductivity.

Ionic conductivity and glass transition of phosphoric acids

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

Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan

2013-01-01

Here we report the low-temperature dielectric and viscoelastic properties of phosphoric acids in the range of H2O:P2O5 1.5 5. Both dielectric and viscosity measurements allow us to determine the glass-transition temperatures of phosphoric acids. The obtained glass-transition temperatures are in good agreement with previous differential scanning calorimetric measurements. Moreover, our analysis reveals moderate decoupling of ionic conductivity from structural relaxation in the vicinity of the glass transition.

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

The chemical identity of intervessel pit membranes in Acer challenges hydrogel control of xylem hydraulic conductivity

PubMed Central

Klepsch, Matthias M.; Schmitt, Marco; Paul Knox, J.; Jansen, Steven

2016-01-01

Ion-mediated enhancement of the hydraulic conductivity of xylem tissue (i.e. the ionic effect) has been reported for various angiosperm species. One explanation of the ionic effect is that it is caused by the swelling and shrinking of intervessel pit membranes due to the presence of pectins and/or other cell-wall matrix polymers such as heteroxylans or arabinogalactan–proteins (AGPs) that may contain acidic sugars. Here, we examined the ionic effect for six Acer species and their pit membrane chemistry using immunocytochemistry, including antibodies against glycoproteins. Moreover, anatomical features related to the bordered pit morphology and vessel dimensions were investigated using light and electron microscopy. The ionic effect varied from 18 % (± 9) to 32 % (± 13). Epitopes of homogalacturonan (LM18) and xylan (LM11) were not detected in intervessel pit membranes. Negative results were also obtained for glycoproteins (extensin: LM1, JIM20; AGP glycan: LM2), although AGP (JIM13)-related epitopes were detected in parenchyma cells. The mean vessel length was significantly correlated with the magnitude of the ionic effect, unlike other pit or vessel-related characteristics. Our results suggest that intervessel pit membranes of Acer are unlikely to contain pectic or other acidic polysaccharides. Therefore, alternative explanations should be tested to clarify the ionic effect. PMID:27354661

Sr- and Nb-co-doped Li7La3Zr2O12 solid electrolyte with Al2O3 addition towards high ionic conductivity

NASA Astrophysics Data System (ADS)

Lin, Changwei; Tang, Yu; Song, Jun; Han, Lei; Yu, Jingbo; Lu, Anxian

2018-06-01

In the present study, series of garnet-type Li6.75+ x La3- x Sr x Zr1.75Nb0.25O12 solid electrolytes [LLSZN with various Sr contents ( x = 0.05-0.25)] have been prepared via conventional solid-state method. The effects of Sr contents on their phase structure and ionic conductivity have been systematically investigated on the combined measurements of X-ray diffraction and scanning electron microscopy and alter current impedance spectroscopy. Our results reveal that a phase transition from tetragonal to cubic structure occurs when both Sr and Nb elements is introduced, and such a cubic structure can be stable over the whole Sr contents variation, which is suggested to provide a beneficial impact on the performance of LLSZN. Accordingly, both relative density and total ionic conductivity exhibit a favorable tendency of increasing first and then decreasing with increased Sr contents, wherein a peak value at 93.46% and 5.09 × 10-4 S cm-1, respectively, can be well achieved. Particularly, the maximum ionic conductivity is almost twice that of the compared sample (2.93 × 10-4 S cm-1), and possess the minimum activation energy 0.30 eV. Such a modification method, featured with higher efficiency and lower cost, is expected to be helpful for the development of solid electrolyte.

Understanding transport mechanisms in ionic liquid/carbonate solvent electrolyte blends.

PubMed

Oldiges, K; Diddens, D; Ebrahiminia, M; Hooper, J B; Cekic-Laskovic, I; Heuer, A; Bedrov, D; Winter, M; Brunklaus, G

2018-06-20

To unravel mechanistic details of the ion transport in liquid electrolytes, blends of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), ethylene carbonate (EC) and dimethyl carbonate (DMC) with the conducting salts lithium hexafluorophosphate (LiPF6) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated as a function of the IL concentration. Electrochemical impedance, Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) and Raman spectroscopy supported by Molecular Dynamics (MD) simulations allowed the structural and dynamic correlations of the ion motions to be probed. Remarkably, we identified that though the individual correlations among different ion types exhibit a clear concentration dependence, their net effect is nearly constant throughout the entire concentration range, resulting in approximately equal transport and transference numbers, despite a monitored cross-over from carbonate-based lithium coordination to a TFSI-based ion coordination. In addition, though dynamical ion correlation could be found, the absolute values of the ionic conductivity are essentially determined by the overall viscosity of the electrolyte. The IL/carbonate blends with a Pyr14TFSI fraction of ∼10 wt% are found to be promising electrolyte solvents, with ionic conductivities and lithium ion transference numbers comparable to those of standard carbonate-based electrolytes while the thermal and electrochemical stabilities are considerably improved. In contrast, the choice of the conducting salt only marginally affects the transport properties.

Ionic conductivity of binary fluorides of potassium and rare earth elements

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

Sorokin, N. I., E-mail: nsorokin1@yandex.ru

2016-01-15

The ionic conductivity s of KYF{sub 4} and K{sub 2}RF{sub 5} single crystals (R = Gd, Ho, Er) and KNdF{sub 4} and K{sub 2}RF{sub 5} ceramic samples (R = Dy, Er) has been studied in the temperature range of 340–500°C. A comparative analysis of the σ values for these objects has been performed. Binary fluorides of potassium and rare earth elements were synthesized by the hydrothermal method (temperature 480°C, pressure 100–150 MPa) in the R{sub 2}O{sub 3}–KF–H{sub 2}O systems. The σ values of tetraf luorides are 3 × 10{sup –5} S/cm (KYF{sub 4} single crystal) and 3 × 10{sup –6}more » S/cm (KNdF{sub 4} ceramics) at 435°C. A K{sub 2}ErF{sub 5} single crystal with σ = 1.2 × 10{sup –4} S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K{sub 2}HoF{sub 5} single crystals, σ{sub ∥c}/σ{sub ⊥c} = 2.5, where σ{sub ∥c} and σ{sub ⊥c} are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.« less

Structural manipulation approaches towards enhanced sodium ionic conductivity in Na-rich antiperovskites

DOE PAGES

Wang, Yonggang; Wang, Qingfei; Liu, Zhenpu; ...

2015-06-10

High-performance solid electrolytes are critical for realizing all-solid-state batteries with enhance safety and cycling efficiency. However, currently available candidates (sulfides and the NASICON-typ ceramics) still suffer from drawbacks such as inflammability, high-cost and unfavorable machinability Here we present the structural manipulation approaches to improve the sodium ionic conductivity in series of affordable Na-rich antiperovskites. Experimentally, the whole solid solutions of Na 3OX (X ¼ Cl Br, I) are synthesized via a facile and timesaving route from the cheapest raw materials (Na, NaOH an NaX). The materials are nonflammable, suitable for thermoplastic processing due to low melting temperature (<300° C) withoutmore » decomposing. Notably, owing to the flexibility of perovskite-type structure it's feasible to control the local structure features by means of size-mismatch substitution an unequivalent-doping for a favorable sodium ionic diffusion pathway. Enhancement of sodium ioni conductivity by 2 magnitudes is demonstrated by these chemical tuning methods. The optimized sodiu ionic conductivity in Na 2.9Sr 0.05OBr 0.6I 0.4 bulk samples reaches 1.9 10 - 3 S/cm at 200° C and even highe at elevated temperature. Here, we believe further chemical tuning efforts on Na-rich antiperovskites wil promote their performance greatly for practical all-solid state battery applications.« less

Thermal conductivity in Bi0.5Sb1.5Te3+x and the role of dense dislocation arrays at grain boundaries.

PubMed

Deng, Rigui; Su, Xianli; Zheng, Zheng; Liu, Wei; Yan, Yonggao; Zhang, Qingjie; Dravid, Vinayak P; Uher, Ctirad; Kanatzidis, Mercouri G; Tang, Xinfeng

2018-06-01

Several prominent mechanisms for reduction in thermal conductivity have been shown in recent years to improve the figure of merit for thermoelectric materials. Such a mechanism is a hierarchical all-length-scale architecturing that recognizes the role of all microstructure elements, from atomic to nano to microscales, in reducing (lattice) thermal conductivity. In this context, there have been recent claims of remarkably low (lattice) thermal conductivity in Bi 0.5 Sb 1.5 Te 3 that are attributed to seemingly ordinary grain boundary dislocation networks. These high densities of dislocation networks in Bi 0.5 Sb 1.5 Te 3 were generated via unconventional materials processing with excess Te (which formed liquid phase, thereby facilitating sintering), followed by spark plasma sintering under pressure to squeeze out the liquid. We reproduced a practically identical microstructure, following practically identical processing strategies, but with noticeably different (higher) thermal conductivity than that claimed before. We show that the resultant microstructure is anisotropic, with notable difference of thermal and charge transport properties across and along two orthonormal directions, analogous to anisotropic crystals. Thus, we believe that grain boundary dislocation networks are not the primary cause of enhanced ZT through reduction in thermal conductivity. Instead, we can reproduce the purported high ZT through a favorable but impractical and incorrect combination of thermal conductivity measured along the pressing direction of anisotropy while charge transport measured in the direction perpendicular to the anisotropic direction. We believe that our work underscores the need for consistency in charge and thermal transport measurements for unified and verifiable measurements of thermoelectric (and related) properties and phenomena.

Effects of High-pH and High-Ionic-Strength Groundwater on Iodide, Pertechnetate, and Selenate Sorption to Hanford Sediments: Final Report for Subtask 3a

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

DI Kaplan; KE Parker; RD Orr

1998-10-14

As part of the Immobilized Low-Activity Waste-Performance Assessment three experiments were conducted to evaluate the effect of the expected near-field chemistry on the sorption of iodide, selenate, and pertechnetate onto a sediment obtained from the Hanford Site. These experiments were performed in fiscal year 1998 at the Pacific Northwest National Laboratory.' During these experiments, attention was directed at the identification of the chemical mechanisms controlling the sorption processes to provide technical defensibility for the selection of the distribution coefficients (IQ to be used in the remainder of the performance assessment. It was found, during the conduct of the experiments, thatmore » selenium and technetium I&s increased as ionic strength increased. The cause for this is most likely to be that the higher ionic strength caused the double layer around the particles to decrease, thereby permitting greater interaction with the mineral surfaces. Further, the pH level had an effect on the sorption of these anions. These are the first-ever experiments conducted with Hanford Site sediment in which the IQ were measured as a function of ionic strength and pH. Overall, the observed trends were consistent with more generalized geochemical principles. One of the most important contributions of these experiments was that they quantified the & changes induced by variations in ionic strength and pH that are expected to exist in the near field.« less

Photochemical formation of chitosan-stabilized near-infrared-absorbing silver Nanoworms: A "Green" synthetic strategy and activity on Gram-negative pathogenic bacteria.

PubMed

Marpu, Sreekar; Kolailat, Samar S; Korir, Daniel; Kamras, Brian L; Chaturvedi, Ratnesh; Joseph, Abel; Smith, Christopher M; Palma, Misael C; Shah, Jyoti; Omary, Mohammad A

2017-12-01

A facile, single-step, non-seeded photochemical protocol for producing a new type of anisotropic silver nanostructure, "nanoworms", with curved longer dimensions and smooth, rounded edges. The nanoworms exhibit surface plasmon resonance (SPR) absorption in the near-infrared window (NIRW) region and are stabilized using biocompatible polymer chitosan, rendering biocompatibility and amplified safety for biological utility of the composition. Both NIRW-absorbing nanoworms and visible-absorbing nanospheres herein are attained exclusively by employing green chemistry principles. Contrary to seed-mediated or polyol techniques, the protocol demonstrates the feasibility to selectively synthesize NIRW-absorbing silver nanostructures in a single step and in complete absence of any known reducing agent. The effect of irradiation, pH, and concentration of starting materials on the formation of nanoworms vs nanospheres is investigated in detail and analyzed by optical spectroscopy and electron microscopy. The dominant SPR obtained in the NIRW region of the nanoworms results from anisotropic AgNPs, as opposed to agglomeration. From TEM images, it is also very clear that a strong correlation exists between the SPR peak maximum and the size distribution of the anisotropic nanoworm structures, with SPR peak maximum exhibiting red shift with the increase in the size of the nanoworm population. Although there is significant size variation of different nanoworms of a given population, all samples exhibit remarkable stability. The nanoworms retained their NIRW-absorbing features even at physiological pH and at a constant ionic strength. The nanodispersions also retained their SPR features in King's B medium. Antipathogenic assays reveal that the anisotropic NIRW-absorbing nanoworms exhibit the highest growth inhibition compared to other spherical nanosilver and molecular silver forms on Gram-negative pathogenic bacteria, Pseudomonas syringae pv. maculicola ES4326 and P. syringae pv. tomato DC3000. These results underscore shape effects of AgNPs and suggest that nanoworms favor the adhesion to (curved) rod-shaped Gram-negative bacteria, resulting in the highest inhibition compared to isotropic AgNPs (smaller spheres), sulfa antibiotics (silver sulfadiazine), and silver ions (AgNO 3 ). Copyright © 2017 Elsevier Inc. All rights reserved.

Composite Solid Electrolyte For Lithium Cells

NASA Technical Reports Server (NTRS)

Peled, Emmanuel; Nagasubramanian, Ganesan; Halpert, Gerald; Attia, Alan I.

1994-01-01

Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

Canonical decomposition of magnetotelluric responses: Experiment on 1D anisotropic structures

NASA Astrophysics Data System (ADS)

Guo, Ze-qiu; Wei, Wen-bo; Ye, Gao-feng; Jin, Sheng; Jing, Jian-en

2015-08-01

Horizontal electrical heterogeneity of subsurface earth is mostly originated from structural complexity and electrical anisotropy, and local near-surface electrical heterogeneity will severely distort regional electromagnetic responses. Conventional distortion analyses for magnetotelluric soundings are primarily physical decomposition methods with respect to isotropic models, which mostly presume that the geoelectric distribution of geological structures is of local and regional patterns represented by 3D/2D models. Due to the widespread anisotropy of earth media, the confusion between 1D anisotropic responses and 2D isotropic responses, and the defects of physical decomposition methods, we propose to conduct modeling experiments with canonical decomposition in terms of 1D layered anisotropic models, and the method is one of the mathematical decomposition methods based on eigenstate analyses differentiated from distortion analyses, which can be used to recover electrical information such as strike directions, and maximum and minimum conductivity. We tested this method with numerical simulation experiments on several 1D synthetic models, which turned out that canonical decomposition is quite effective to reveal geological anisotropic information. Finally, for the background of anisotropy from previous study by geological and seismological methods, canonical decomposition is applied to real data acquired in North China Craton for 1D anisotropy analyses, and the result shows that, with effective modeling and cautious interpretation, canonical decomposition could be another good method to detect anisotropy of geological media.

Hetero-phase fluctuations in the pre-melting region in ionic crystals

NASA Astrophysics Data System (ADS)

Matsunaga, S.; Tamaki, S.

2008-06-01

The theory of the pre-melting phenomena in ionic crystals on the basis of the concept of the hetero phase fluctuation has been applied to KCl and AgCl crystal. The large scale molecular dynamics simulations (MD) in KCl and AgCl crystals are also performed to examine the ionic configuration in premelting region in the vicinity of their melting points. The size of the liquid like clusters are estimated by the theory and MD. The structural features of liquid like clusters are discussed by MD results using the Lindemann instability condition. The ionic conductivities in the pre-melting region are also discussed on the same theoretical basis.

A novel anisotropic fast marching method and its application to blood flow computation in phase-contrast MRI.

PubMed

Schwenke, M; Hennemuth, A; Fischer, B; Friman, O

2012-01-01

Phase-contrast MRI (PC MRI) can be used to assess blood flow dynamics noninvasively inside the human body. The acquired images can be reconstructed into flow vector fields. Traditionally, streamlines can be computed based on the vector fields to visualize flow patterns and particle trajectories. The traditional methods may give a false impression of precision, as they do not consider the measurement uncertainty in the PC MRI images. In our prior work, we incorporated the uncertainty of the measurement into the computation of particle trajectories. As a major part of the contribution, a novel numerical scheme for solving the anisotropic Fast Marching problem is presented. A computing time comparison to state-of-the-art methods is conducted on artificial tensor fields. A visual comparison of healthy to pathological blood flow patterns is given. The comparison shows that the novel anisotropic Fast Marching solver outperforms previous schemes in terms of computing time. The visual comparison of flow patterns directly visualizes large deviations of pathological flow from healthy flow. The novel anisotropic Fast Marching solver efficiently resolves even strongly anisotropic path costs. The visualization method enables the user to assess the uncertainty of particle trajectories derived from PC MRI images.

Anisotropic electrical conduction and reduction in dangling-bond density for polycrystalline Si films prepared by catalytic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Niikura, Chisato; Masuda, Atsushi; Matsumura, Hideki

1999-07-01

Polycrystalline Si (poly-Si) films with high crystalline fraction and low dangling-bond density were prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD. Directional anisotropy in electrical conduction, probably due to structural anisotropy, was observed for Cat-CVD poly-Si films. A novel method to separately characterize both crystalline and amorphous phases in poly-Si films using anisotropic electrical conduction was proposed. On the basis of results obtained by the proposed method and electron spin resonance measurements, reduction in dangling-bond density for Cat-CVD poly-Si films was achieved using the condition to make the quality of the included amorphous phase high. The properties of Cat-CVD poly-Si films are found to be promising in solar-cell applications.

Static and transport properties of alkyltrimethylammonium cation-based room-temperature ionic liquids.

PubMed

Seki, Shiro; Tsuzuki, Seiji; Hayamizu, Kikuko; Serizawa, Nobuyuki; Ono, Shimpei; Takei, Katsuhito; Doi, Hiroyuki; Umebayashi, Yasuhiro

2014-05-01

We have measured physicochemical properties of five alkyltrimethylammonium cation-based room-temperature ionic liquids and compared them with those obtained from computational methods. We have found that static properties (density and refractive index) and transport properties (ionic conductivity, self-diffusion coefficient, and viscosity) of these ionic liquids show close relations with the length of the alkyl chain. In particular, static properties obtained by experimental methods exhibit a trend complementary to that by computational methods (refractive index ∝ [polarizability/molar volume]). Moreover, the self-diffusion coefficient obtained by molecular dynamics (MD) simulation was consistent with the data obtained by the pulsed-gradient spin-echo nuclear magnetic resonance technique, which suggests that computational methods can be supplemental tools to predict physicochemical properties of room-temperature ionic liquids.

IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

EPA Science Inventory

A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

Charge carrier dynamics and relaxation in (polyethylene oxide-lithium-salt)-based polymer electrolyte containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide as ionic liquid

NASA Astrophysics Data System (ADS)

Karmakar, A.; Ghosh, A.

2011-11-01

In this paper we report the dynamics of charge carriers and relaxation in polymer electrolytes based on polyethylene oxide (PEO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) ionic liquid prepared by solution cast technique. It has been observed that the incorporation of BMPTFSI into PEO-LiTFSI electrolyte is an effective way for increasing the amorphous phase to a large extent. It has also been observed that both the glass transition and melting temperatures decrease with the increase of BMPTFSI concentration. The ionic conductivity of these polymer electrolytes increases with the increase of BMPTFSI concentration. The highest ionic conductivity obtained at 25 °C is ˜3×10-4 S cm-1 for the electrolyte containing 60 wt % BMPTFSI and ethylene oxide (EO)/Li ratio of 20. The temperature dependence of the dc conductivity and the hopping frequency show Vogel-Tamman-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The frequency dependence of the ac conductivity exhibits a power law with an exponent n which decreases with the increase of temperature. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and BMPTFSI concentrations. We have also presented the electric modulus data which have been analyzed in the framework of a Havriliak-Negami equation and the shape parameters obtained by the analysis show slight temperature dependence, but change sharply with BMPTFSI concentration. The stretched exponent β obtained from Kohlrausch-Williams-Watts fit to the modulus data is much lower than unity signifying that the relaxation is highly nonexponential. The decay function obtained from analysis of experimental modulus data is highly asymmetric with time.

Embedding of polyaniline molecules on adhesive tape using successive ionic layer adsorption and reaction (SILAR) technique

NASA Astrophysics Data System (ADS)

Pamatmat, J. K.; Gillado, A. V.; Herrera, M. U.

2017-05-01

Polyaniline molecules are embedded on adhesive tape using successive ionic layer adsorption and reaction (SILAR) technique. The infrared spectrum shows the existence of molecular vibrational modes associated with the presence of polyaniline molecules on the sample. With the addition of polyaniline molecules, the conductivity of adhesive tape increases. Surface conductivity increases with number of dipping cycle until it reaches a certain value. Beyond this value, surface conductivity begins to decrease. The surface conductivity of the sample is associated with the connectivity of the embedded polyaniline molecules. The connectivity increases as the number of dipping cycle progresses. Meanwhile, the decrease in surface conductivity is attributed to the eroding of existing embedded structure at higher number of dipping cycle.

Speckle-reducing scale-invariant feature transform match for synthetic aperture radar image registration

NASA Astrophysics Data System (ADS)

Wang, Xianmin; Li, Bo; Xu, Qizhi

2016-07-01

The anisotropic scale space (ASS) is often used to enhance the performance of a scale-invariant feature transform (SIFT) algorithm in the registration of synthetic aperture radar (SAR) images. The existing ASS-based methods usually suffer from unstable keypoints and false matches, since the anisotropic diffusion filtering has limitations in reducing the speckle noise from SAR images while building the ASS image representation. We proposed a speckle reducing SIFT match method to obtain stable keypoints and acquire precise matches for the SAR image registration. First, the keypoints are detected in a speckle reducing anisotropic scale space constructed by the speckle reducing anisotropic diffusion, so that speckle noise is greatly reduced and prominent structures of the images are preserved, consequently the stable keypoints can be derived. Next, the probabilistic relaxation labeling approach is employed to establish the matches of the keypoints then the correct match rate of the keypoints is significantly increased. Experiments conducted on simulated speckled images and real SAR images demonstrate the effectiveness of the proposed method.

Models of collapsing and expanding anisotropic gravitating source in f( R, T) theory of gravity

NASA Astrophysics Data System (ADS)

Abbas, G.; Ahmed, Riaz

2017-07-01

In this paper, we have formulated the exact solutions of the non-static anisotropic gravitating source in f( R, T) gravity which may lead to expansion and collapse. By assuming there to be no thermal conduction in gravitating source, we have determined parametric solutions in f( R, T) gravity with a non-static spherical geometry filled using an anisotropic fluid. We have examined the ranges of the parameters for which the expansion scalar becomes negative and positive, leading to collapse and expansion, respectively. Further, using the definition of the mass function, the conditions for the trapped surface have been explored, and it has been investigated that there exists a single horizon in this case. The impact of the coupling parameter λ has been discussed in detail in both cases. For the various values of the coupling parameter λ , we have plotted the energy density, anisotropic pressure and anisotropy parameter in the cases of collapse and expansion. The physical significance of the graphs has been explained in detail.

Measurement of Anisotropic Particle Interactions with Nonuniform ac Electric Fields.

PubMed

Rupp, Bradley; Torres-Díaz, Isaac; Hua, Xiaoqing; Bevan, Michael A

2018-02-20

Optical microscopy measurements are reported for single anisotropic polymer particles interacting with nonuniform ac electric fields. The present study is limited to conditions where gravity confines particles with their long axis parallel to the substrate such that particles can be treated using quasi-2D analysis. Field parameters are investigated that result in particles residing at either electric field maxima or minima and with long axes oriented either parallel or perpendicular to the electric field direction. By nonintrusively observing thermally sampled positions and orientations at different field frequencies and amplitudes, a Boltzmann inversion of the time-averaged probability of states yields kT-scale energy landscapes (including dipole-field, particle-substrate, and gravitational potentials). The measured energy landscapes show agreement with theoretical potentials using particle conductivity as the sole adjustable material property. Understanding anisotropic particle-field energy landscapes vs field parameters enables quantitative control of local forces and torques on single anisotropic particles to manipulate their position and orientation within nonuniform fields.

Enhanced ionic conductivity of AgI nanowires/AAO composites fabricated by a simple approach.

PubMed

Liu, Li-Feng; Lee, Seung-Woo; Li, Jing-Bo; Alexe, Marin; Rao, Guang-Hui; Zhou, Wei-Ya; Lee, Jae-Jong; Lee, Woo; Gösele, Ulrich

2008-12-10

AgI nanowires/anodic aluminum oxide (AgI NWs/AAO) composites have been fabricated by a simple approach, which involves the thermal melting of AgI powders on the surface of the AAO membrane, followed by the infiltration of the molten AgI inside the nanochannels. As-prepared AgI nanowires have corrugated outer surfaces and are polycrystalline according to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. X-ray diffraction (XRD) shows that a considerable amount of 7H polytype AgI exists in the composites, which is supposed to arise from the interfacial interactions between the embedded AgI and the alumina. AC conductivity measurements for the AgI nanowires/AAO composites exhibit a notable conductivity enhancement by three orders of magnitude at room temperature compared with that of pristine bulk AgI. Furthermore, a large conductivity hysteresis and abnormal conductivity transitions were observed in the temperature-dependent conductivity measurements, from which an ionic conductivity as high as 8.0 × 10(2) Ω(-1) cm(-1) was obtained at around 70 °C upon cooling. The differential scanning calorimetry (DSC) result demonstrates a similar phase transition behavior as that found in the AC conductivity measurements. The enhanced ionic conductivity, as well as the abnormal phase transitions, can be explained in terms of the existence of the highly conducting 7H polytype AgI and the formation of well-defined conduction paths in the composites.

The anisotropic tunneling behavior of spin transport in graphene-based magnetic tunneling junction

NASA Astrophysics Data System (ADS)

Pan, Mengchun; Li, Peisen; Qiu, Weicheng; Zhao, Jianqiang; Peng, Junping; Hu, Jiafei; Hu, Jinghua; Tian, Wugang; Hu, Yueguo; Chen, Dixiang; Wu, Xuezhong; Xu, Zhongjie; Yuan, Xuefeng

2018-05-01

Due to the theoretical prediction of large tunneling magnetoresistance (TMR), graphene-based magnetic tunneling junction (MTJ) has become an important branch of high-performance spintronics device. In this paper, the non-collinear spin filtering and transport properties of MTJ with the Ni/tri-layer graphene/Ni structure were studied in detail by utilizing the non-equilibrium Green's formalism combined with spin polarized density functional theory. The band structure of Ni-C bonding interface shows that Ni-C atomic hybridization facilitates the electronic structure consistency of graphene and nickel, which results in a perfect spin filtering effect for tri-layer graphene-based MTJ. Furthermore, our theoretical results show that the value of tunneling resistance changes with the relative magnetization angle of two ferromagnetic layers, displaying the anisotropic tunneling behavior of graphene-based MTJ. This originates from the resonant conduction states which are strongly adjusted by the relative magnetization angles. In addition, the perfect spin filtering effect is demonstrated by fitting the anisotropic conductance with the Julliere's model. Our work may serve as guidance for researches and applications of graphene-based spintronics device.

Method of making a layered composite electrode/electrolyte

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-01-25

An electrode/electrolyte structure is prepared by a plurality of methods. An unsintered (possibly bisque fired) moderately catalytic electronically-conductive or homogeneous mixed ionic electronic conductive electrode material is deposited on a layer composed of a sintered or unsintered ionically-conductive electrolyte material prior to being sintered. A layer of particulate electrode material is deposited on an unsintered ("green") layer of electrolyte material and the electrode and electrolyte layers are sintered simultaneously, sometimes referred to as "co-firing," under conditions suitable to fully densify the electrolyte while the electrode retains porosity. Or, the layer of particulate electrode material is deposited on a previously sintered layer of electrolyte, and then sintered. Subsequently, a catalytic material is added to the electrode structure by infiltration of an electrolcatalyst precursor (e.g., a metal salt such as a transition metal nitrate). This may be followed by low temperature firing to convert the precursor to catalyst. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in an ionic (electrochemical) device such as fuel cells and electrolytic gas separation systems.

Characterization of un-plasticized and propylene carbonate plasticized carboxymethyl cellulose doped ammonium chloride solid biopolymer electrolytes.

PubMed

Ahmad, N H; Isa, M I N

2016-02-10

Two solid biopolymer electrolytes (SBEs) systems of carboxymethyl cellulose doped ammonium chloride (CMC-AC) and propylene carbonate plasticized (CMC-AC-PC) were prepared via solution casting technique. The ionic conductivity of SBEs were analyzed using electrical impedance spectroscopy (EIS) in the frequency range of 50 Hz-1 MHz at ambient temperature (303K). The highest ionic conductivity of CMC-AC SBE is 1.43 × 10(-3)S/cm for 16 wt.% of AC while the highest conductivity of plasticized SBE system is 1.01 × 10(-2)S/cm when added with 8 wt.% of PC. TGA/DSC showed that the addition of PC had increased the decomposition temperature compared of CMC-AC SBE. Fourier transform infrared (FTIR) spectra showed the occurrence of complexation between the SBE components and it is proved successfully executed by Gaussian software. X-ray diffraction (XRD) indicated that amorphous nature of SBEs. It is believed that the PC is one of the most promising plasticizer to enhance the ionic conductivity and performance for SBE system. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Variation of Ionic Conductivity with Annealing Temperature in Argyrodite Solid Electrolytes

NASA Astrophysics Data System (ADS)

Rao, R. Prasada; Chen, Maohua; Adams, Stefan

2013-07-01

In situ neutron diffraction studies of argyrodite-type Li6PS5X (X = Cl, Br, I) were conducted for mechanically milled sample to reveal the formation and growth of crystalline phases. These studies indicated the formation of crystals in all the compounds started from as low as 80°C. The Rietveld refinements of the resulting crystalline phases at 150°C indicate the formation of the argyrodite structure. Structure refinements using high-intensity neutron diffraction provide insight into the influence of disorder on the fast ionic conductivity. Besides the disorder in the lithium distribution, it is the disorder in the S2-/Cl- or S2-/Br- distribution that we find to promote ion mobility. Among the samples studied Li6PS5Br, annealed at 250°C, exhibited the highest ionic conductivity, 1.05 × 10-3 S/cm at room temperature. An all solid state battery with Li4Ti5O12/Li6PS5Br/Li exhibited 57 mAh/g first discharge capacity at 75°C with 91% coulombic efficiency after 60 cycles.

Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

2018-03-01

A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

Monitoring sodium removal and delivered dialysis by conductivity.

PubMed

Locatelli, F; Di Filippo, S; Manzoni, C; Corti, M; Andrulli, S; Pontoriero, G

1995-11-01

As cardiovascular stability and the delivery of the prescribed dialysis "dose" seem to be the main factors in determining the morbidity and mortality of hemodialyzer patients today, it is of paramount importance to match hydro-sodium removal with interdialytic load and to verify the delivered dialysis at each session. A specially designed Biofeedback Module (BM--COT Hospal) allows the automatic determination of plasma water conductivity and effective ionic dialysance with no need for blood samples. Using BM, we evaluated the validity of "conductivity kinetic modelling" (CKM) and the possibility that this may substitute "sodium kinetic modelling". Moreover, we evaluated the "in vivo" relationship between ionic dialysance and effective urea clearance. Our results demonstrate that: 1) CKM makes it possible to obtain programmed end-dialysis plasma water conductivity with an error of less than +/- 0.14 mS/cm, roughly equivalent to a sodium concentration of +/- 1.4 mEq/L. 2). Ionic dialysance and effective urea clearance are not equivalent but, as the interrelationship between these is known, the BM allows the routine monitoring of delivered dialysis.

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

PubMed

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

2014-08-13

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

Transport Properties of Ionic Liquid Mixtures Containing Heterodications

DOE PAGES

Lall-Ramnarine, S.; Fernandez, E.; Rodriguez, C.; ...

2016-08-30

This report discusses the transport properties of ionic liquid mixtures that incorporate a series of asymmetrical dications, including heterodications. The dicationic ILs combine either triphenylphosphonium and trimethylammonium cationic sites that are bridged to methylimidazolium or methylpyrrolidinium cationic sites. Mixtures were made of the dicationic bis(trifluoromethylsulfonyl)amide ionic liquids with N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide. The IL mixtures were characterized for their transport properties (temperature dependent conductivity and viscosity) and thermal properties (melting point and glass transition point).

Investigation of Proton Conductivity of Cation-Exchanged, Sulfonated Poly(b-Styrene-b-Isobutylene-b-Styrene) Membranes

DTIC Science & Technology

2009-09-01

solvents. Similar behavior was observed for Nafion -117 (also a polymer with ionic SO3H clusters) by other researchers (14). Results shown in this...pattern was only valid for ionic S-SIBS membranes exchanged with cations; neither acid form of SIBS-97-H nor Nafion -117 fell on this line. In order...10  vi INTENTIONALLY LEFT BLANK. 1 1. Introduction Research in ionic polymers has been gaining popularity in the scientific community

Ionic Conductivity of TlBr1-xIx(x = 0, 0.2, 1): Candidate Gamma Ray Detector

NASA Astrophysics Data System (ADS)

Bishop, S. R.; Ciampi, G.; Lee, C. D.; Kuhn, M.; Tuller, H. L.; Higgins, W.; Shah, K. S.

2012-10-01

The ionic conductivity of TlBr, TlI and their solid solutions, candidates for high energy radiation detection, was examined using impedance spectroscopy. The orthorhombic to cubic phase change in TlI was observed via a steep change in conductivity with increasing temperature, whereas the TlBr-TlI solid solution was cubic throughout the measured temperature range, in agreement with the literature. The intrinsic conductivity of the cubic phase of each material showed nearly identical behavior, indicating that I substitution for Br has little to no effect on the combined defect formation and transport parameters in the studied range. Additionally, optical transmission was correlated with I concentration.

Effect of Al2O3 nanoparticles in plasticized PMMA-LiClO4 based solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2017-05-01

We have studied the broadband complex conductivity spectra covering a 0.01 Hz-3 GHz frequency range for plasticized PMMA-LiClO4 based solid polymer electrolyte embedded with Al2O3 nanoparticle. We have analyzed the conductivity spectra using the random free-energy barrier model (RBM) coupled with electrode polarization contribution in the low frequency region and at high temperatures. The temperature dependence of the ionic conductivity obtained from the analysis has been analyzed using Vogel-Tammann-Fulcher equation. The maximum ionic conductivity ˜ 1.93×10-4 S/cm has been obtained for 1 wt% Al2O3 nanoparticle.

Structural and electrical characterization of tamarind seed polysaccharide (TSP) doped with NH4HCO2

NASA Astrophysics Data System (ADS)

Premalatha, M.; Mathavan, T.; Selvasekarapandian, S.; Selvalakshmi, S.

2018-04-01

In the modern era, development of electrochemical energy devices such as batteries, fuel cells and supercapacitors gain attention due to the deficiency of renewable energy resources. More specifically, proton conducting materials create prime interest in the development of electrochemical devices. In this regards, a novel proton conducting biopolymer electrolyte based on Tamarind Seed Polysaccharide (TSP) was synthesized with different concentration of ammonium formate (NH4HCO2). The amorphous nature of the polymer electrolytes has been identified by XRD technique. The observed ionic conductivity values reveal that the biopolymer containing 1 g TSP: 0.4 g NH4HCO2 has highest ionic conductivity 1.23×10-3 S cm-1.

Composite electrode/electrolyte structure

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2004-01-27

Provided is an electrode fabricated from highly electronically conductive materials such as metals, metal alloys, or electronically conductive ceramics. The electronic conductivity of the electrode substrate is maximized. Onto this electrode in the green state, a green ionic (e.g., electrolyte) film is deposited and the assembly is co-fired at a temperature suitable to fully densify the film while the substrate retains porosity. Subsequently, a catalytic material is added to the electrode structure by infiltration of a metal salt and subsequent low temperature firing. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in ionic (electrochemical) devices such as fuel cells and electrolytic gas separation systems.

Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

DOE PAGES

Farrow, Tim; Yang, Nan; Doria, Sandra; ...

2015-03-17

Spatial variability of conductivity in ceria is explored using scanning probe microscopy with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggest the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunnelingmore » barriers« less

Three-dimensional forward modeling and inversion of marine CSEM data in anisotropic conductivity structures

NASA Astrophysics Data System (ADS)

Han, B.; Li, Y.

2016-12-01

We present a three-dimensional (3D) forward and inverse modeling code for marine controlled-source electromagnetic (CSEM) surveys in anisotropic media. The forward solution is based on a primary/secondary field approach, in which secondary fields are solved using a staggered finite-volume (FV) method and primary fields are solved for 1D isotropic background models analytically. It is shown that it is rather straightforward to extend the isotopic 3D FV algorithm to a triaxial anisotropic one, while additional coefficients are required to account for full tensor conductivity. To solve the linear system resulting from FV discretization of Maxwell' s equations, both iterative Krylov solvers (e.g. BiCGSTAB) and direct solvers (e.g. MUMPS) have been implemented, makes the code flexible for different computing platforms and different problems. For iterative soloutions, the linear system in terms of electromagnetic potentials (A-Phi) is used to precondition the original linear system, transforming the discretized Curl-Curl equations to discretized Laplace-like equations, thus much more favorable numerical properties can be obtained. Numerical experiments suggest that this A-Phi preconditioner can dramatically improve the convergence rate of an iterative solver and high accuracy can be achieved without divergence correction even for low frequencies. To efficiently calculate the sensitivities, i.e. the derivatives of CSEM data with respect to tensor conductivity, the adjoint method is employed. For inverse modeling, triaxial anisotropy is taken into account. Since the number of model parameters to be resolved of triaxial anisotropic medias is twice or thrice that of isotropic medias, the data-space version of the Gauss-Newton (GN) minimization method is preferred due to its lower computational cost compared with the traditional model-space GN method. We demonstrate the effectiveness of the code with synthetic examples.

Electrical resistivity structure of the Great Slave Lake shear zone, northwest Canada: implications for tectonic history

NASA Astrophysics Data System (ADS)

Yin, Yaotian; Unsworth, Martyn; Liddell, Mitch; Pana, Dinu; Craven, James A.

2014-10-01

Three magnetotelluric (MT) profiles in northwestern Canada cross the central and western segments of Great Slave Lake shear zone (GSLsz), a continental scale strike-slip structure active during the Slave-Rae collision in the Proterozoic. Dimensionality analysis indicates that (i) the resistivity structure is approximately 2-D with a geoelectric strike direction close to the dominant geological strike of N45°E and that (ii) electrical anisotropy may be present in the crust beneath the two southernmost profiles. Isotropic and anisotropic 2-D inversion and isotropic 3-D inversions show different resistivity structures on different segments of the shear zone. The GSLsz is imaged as a high resistivity zone (>5000 Ω m) that is at least 20 km wide and extends to a depth of at least 50 km on the northern profile. On the southern two profiles, the resistive zone is confined to the upper crust and pierces an east-dipping crustal conductor. Inversions show that this dipping conductor may be anisotropic, likely caused by conductive materials filling a network of fractures with a preferred spatial orientation. These conductive regions would have been disrupted by strike-slip, ductile deformation on the GSLsz that formed granulite to greenschist facies mylonite belts. The pre-dominantly granulite facies mylonites are resistive and explain why the GSLsz appears as a resistive structure piercing the east-dipping anisotropic layer. The absence of a dipping anisotropic/conductive layer on the northern MT profile, located on the central segment of the GSLsz, is consistent with the lack of subduction at this location as predicted by geological and tectonic models.

Three-body effects in Casimir-Polder repulsion

NASA Astrophysics Data System (ADS)

Milton, Kimball A.; Abalo, E. K.; Parashar, Prachi; Pourtolami, Nima; Brevik, Iver; Ellingsen, Simen Å.; Buhmann, Stefan Yoshi; Scheel, Stefan

2015-04-01

In this paper we study an archetypical scenario in which repulsive Casimir-Polder forces between an atom or molecule and two macroscopic bodies can be achieved. This is an extension of previous studies of the interaction between a polarizable atom and a wedge, in which repulsion occurs if the atom is sufficiently anisotropic and close enough to the symmetry plane of the wedge. A similar repulsion occurs if such an atom passes a thin cylinder or a wire. An obvious extension is to compute the interaction between such an atom and two facing wedges, which includes as a special case the interaction of an atom with a conducting screen possessing a slit, or between two parallel wires. To this end we further extend the electromagnetic multiple-scattering formalism for three-body interactions. To test this machinery we reinvestigate the interaction of a polarizable atom between two parallel conducting plates. In that case, three-body effects are shown to be small and are dominated by three- and four-scattering terms. The atom-wedge calculation is illustrated by an analogous scalar situation, described in the Appendix. The wedge-wedge-atom geometry is difficult to analyze because this is a scale-free problem. However, it is not so hard to investigate the three-body corrections to the interaction between an anisotropic atom or nanoparticle and a pair of parallel conducting cylinders and show that the three-body effects are very small and do not affect the Casimir-Polder repulsion at large distances between the cylinders. Finally, we consider whether such highly anisotropic atoms needed for repulsion are practically realizable. Since this appears rather difficult to accomplish, it may be more feasible to observe such effects with highly anisotropic nanoparticles.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2016-07-01

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

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

Pal, P.; Ghosh, A., E-mail: sspag@iacs.res.in

2016-07-28

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamicsmore » of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.« less

Density Optimization of Lithium Lanthanum Titanate Ceramics for Lightweight Lithium-Air Batteries

DTIC Science & Technology

2014-11-01

Thangadurai V, Weppner W. Lithium lanthanum titanates: a review. Chemistry of Materials. 2003;15:3974–3990. 4. Knauth P. Inorganic solid Li ion conductors...an overview. Solid State Ionics. 2009;180:911–916. 5. Ban CW, Choi GM. The effect of sintering on the grain boundary conductivity of lithium ...lanthanum titanates. Solid State Ionics. 2001;140:285–292. 6. Inada R, Kimura K, Kusakabe K, Tojo T, Sakurai Y. Synthesis and lithium -ion conductivity

Oxyphosphorus-containing polymers as binders for battery cathodes

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

Pratt, Russell Clayton; Mullin, Scott Allen; Eitouni, Hany Basam

A class of polymeric phosphorous esters can be used as binders for battery cathodes. Metal salts can be added to the polymers to provide ionic conductivity. The polymeric phosphorous esters can be formulated with other polymers either as mixtures or as copolymers to provide additional desirable properties. Examples of such properties include even higher ionic conductivity and improved mechanical properties. Furthermore, cathodes that include the polymeric phosphorous esters can be assembled with a polymeric electrolyte separator and an anode to form a complete battery.

Study of Parameters Dominating Electromechanical and Sensing Response in Ionic Electroactive Polymer (IEAP) Transducers

NASA Astrophysics Data System (ADS)

Almomani, Abdallah Mohammad

Ionic electroactive polymer (IEAP) transducers are a class of smart structures based on polymers that can be designed as soft actuators or sensors. IEAP actuators exhibit a high mechanical response to an external electrical stimulus. Conversely, they produce electrical signals when subjected to mechanical force. IEAP transducers are mainly composed of four different components: The ionomeric membrane (usually Nafion) is an ion permeable polymer that acts as the backbone of the transducer. Two conductive network composite (CNC) layer on both sides of the ionomeric membrane that enhance the surface conductivity and serve as an extra reservoir to the electrolytes. The electrolytes, (usually ionic liquids (IL)), which provides the mobile ions. And two outer electrodes on both sides of the transducer to either provide a distributed applied potential across the actuators (usually gold leaves) or to collect the generated signals from the sensors (usually copper electrodes). Any variation in any of these components or the operating conditions will directly affect the performance of the IEAP transduces. In this dissertation, we studied some of the parameters dominating the performance of the IEAP transducers by varying some of the transducers components or the transducers operating conditions in order to enhance their performance. The first study was conducted to understand the influence of ionic liquid concentration on the electromechanical performance of IEAP actuators. The IL weight percentage (wt%) was varied from 10% to 30% and both the electromechanical (induced strain) and the electrochemical (the current flow across the actuators) were studied. The results from this study showed an enhanced electrochemical performance (current flow is higher for higher IL wt%) and a maximum electromechanical strain of approximately 1.4% at 22 wt% IL content. A lower induced strain was noticed for IL wt% lower or higher than 22%. The second study was to investigate the effect of changing the morphology of the CNC on the sensing performance of IEAP stress sensors. In this study, small salt molecules were added to the CNC layers. Salt molecules directly affected the morphology of the CNC layers resulting in a thicker, more porous, and high conductive CNCs. As a result, the ionic conductivity increased through the CNC layers and sensing performance was enhanced significantly. In the third study, a non-linear angular deformation (limb-like motion) was achieved by varying the CNC layers of the IEAP actuators by adding some conjugated polymers (CP) patterns during the fabrication of the actuators. It was found that the segments with the CP layers will only expand and never contract during the actuation process. Depending on the direction of motion and the location of the CP layers, different actuation shapes such as square or triangular shapes were achieved rather than the typical circular bending. In the fourth study, the influence of temperature on the electromechanical properties of the IEAP actuators was examined. In this study, both electromechanical and electrochemical studies were conducted for actuators that were operated at temperatures ranging from 25 °C to 90 °C. The electromechanical results showed a lower cationic curvature with increasing temperature up to 70 °C. On the other hand, a maximum anionic curvature was achieved at 50 °C with a sudden decrease after 50 °C. Actuators started to lose functionality and showed unpredictable performance at temperatures higher than 70 °C. Electrochemically, an enhancement of the ionic conductivity was resulted from increasing temperature up to 80 °C. A sudden increase in current flow was recorded at 90 °C indicating a shorted circuit and actuator failure. Finally, in the fifth study, protons in Nafion membranes were exchanged with other counterions of different Van der Waals volumes. The ionic conductivity was measured for IEAP membranes with different counterions at different temperatures. The results showed higher ionic conductivities across membranes with larger Van der Waals volume counterions and higher temperatures. A different ionic conductivity behavior was also noticed for temperatures ranging from 30 °C to 55 °C than temperatures between 55 °C and 70 °C after fitting the data with the Arrhenius conductivity equation.

Computational and experimental investigation of Li-doped ionic liquid electrolytes: [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4].

PubMed

Haskins, Justin B; Bennett, William R; Wu, James J; Hernández, Dionne M; Borodin, Oleg; Monk, Joshua D; Bauschlicher, Charles W; Lawson, John W

2014-09-25

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 ≤ xLi(+) ≤ 0.33) and temperature (298 K ≤ T ≤ 393 K). Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi(+) we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD simulations and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi(+), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi(+) = 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 and 0.3 mS/cm. Our transport results also demonstrate the necessity of long MD simulation runs (∼200 ns) to converge transport properties at room temperature. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions (τ(Li/-)), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li(+) transport in each liquid, we find that while the net motion of Li(+) with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange increases at high xLi(+) and in liquids with large anions.

Scaling Behavior for Ionic Transport and its Fluctuations in Individual Carbon Nanotubes.

PubMed

Secchi, Eleonora; Niguès, Antoine; Jubin, Laetitia; Siria, Alessandro; Bocquet, Lydéric

2016-04-15

In this Letter, we perform an experimental study of ionic transport and current fluctuations inside individual carbon nanotubes (CNTs). The conductance exhibits a power law behavior at low salinity, with an exponent close to 1/3 versus the salt concentration in this regime. This behavior is rationalized in terms of a salinity dependent surface charge, which is accounted for on the basis of a model for hydroxide adsorption at the (hydrophobic) carbon surface. This is in contrast to boron nitride nanotubes which exhibit a constant surface conductance. Further, we measure the low frequency noise of the ionic current in CNTs and show that the amplitude of the noise scales with the surface charge, with data collapsing on a master curve for the various studied CNTs at a given pH.

Scaling Behavior for Ionic Transport and its Fluctuations in Individual Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Secchi, Eleonora; Niguès, Antoine; Jubin, Laetitia; Siria, Alessandro; Bocquet, Lydéric

2016-04-01

In this Letter, we perform an experimental study of ionic transport and current fluctuations inside individual carbon nanotubes (CNTs). The conductance exhibits a power law behavior at low salinity, with an exponent close to 1 /3 versus the salt concentration in this regime. This behavior is rationalized in terms of a salinity dependent surface charge, which is accounted for on the basis of a model for hydroxide adsorption at the (hydrophobic) carbon surface. This is in contrast to boron nitride nanotubes which exhibit a constant surface conductance. Further, we measure the low frequency noise of the ionic current in CNTs and show that the amplitude of the noise scales with the surface charge, with data collapsing on a master curve for the various studied CNTs at a given p H .

Electrical properties of binary mixtures of amino silicone oil and methyl iso butyl ketone

NASA Astrophysics Data System (ADS)

Shah, K. N.; Rana, V. A.; Vankar, H. P.

2018-05-01

The real and imaginary parts of the dielectric function of the binary mixtures of the methyl iso butyl ketone and amino silicone oil in the frequency range 100 Hz to 2 MHz were measured using precision LCR meter at 305.15 K. The electrical properties such as electrical modulus M*(ω), electrical conductivity σ*(ω) and complex impedance Z*(ω) were calculated using the dielectric function ɛ*(ω). The ionic polarization relaxation time (Τσ) and D.C. conductivity (σdc) were also calculated using electrical properties. The ionic behavior of methyl iso butyl ketone and non-ionic behavior of amino silicone oil are also explained. The electrical parameters are used to gain information about the effect of concentration variation of components of the mixtures on the electrical properties.

Innovative Ionic Liquids: Electrolytes for Ion Power Sources

DTIC Science & Technology

2008-01-01

imide–based ILs can function not only as the electrolyte in a conventional lithium ion battery , but also as a solid nanocomposite separator when...conductivity comparable to the pure ionic liquid. Figure 6 shows the charge-discharge behavior of the micro lithium ion battery created entirely by the

The use of stable isotope to evaluate water mixing and water use by flood plain trees along the Garonne valley

USGS Publications Warehouse

Lambs, L.; Loubiat, M.; Richardson, W.

2003-01-01

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (??18O: -9.1??? to -9.0???, conductivity: 217-410??S/cm) was distinctly different from groundwater (??18O: -7.1??? to -6.6???, conductivity: 600-900??S/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (1m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.

Formation and anisotropic magnetoresistance of Co/Pt nano-contacts through aluminum oxide barrier

NASA Astrophysics Data System (ADS)

Al-Mahdawi, Muftah; Sahashi, Masashi

2014-01-01

We report on the observation of anisotropic magnetoresistance (AMR) in vertical asymmetric nano-contacts (NCs) made through AlOx nano-oxide layer (NOL) formed by ion-assisted oxidation method in the film stack of Co/AlOx-NOL/Pt. Analysis of NC formation was based on in situ conductive atomic force microscopy and transmission electron microscopy. Depending on the purity of NCs from Al contamination, we observed up to 29% AMR ratio at room temperature.