Ion exchange kinetics of polycrystalline Na/Kβ/β″-Al2O3

The ion exchange kinetics of polycrystalline Na/K β/β″-Al₂O₃ soaked in H₂SO₄ were studied. The rate of ion exchange in hot concentrated H₂SO₄ was determined by monitoring the change of solution alkali content. The H₃O⁺ diffusion coefficient was estimated from the resulting time dependence data and the ceramic conductivity calculated. Dilute H₂SO₄ with a constant applied voltage was also studied and the ceramic conductivity calculated from the change of current with time. The estimated conductivities obtained by the two methods are compared with reported values for H₃O⁺-β- and β″-Al₂O₃ single crystals. Utilising an H₃O⁺ jump model, the estimated values reflect intragranular conduction.     

Conductivity of β″ and ion rich β alumina.I.H.+(H2O)n compounds

The conductivity and thermal stability of H⁺(H₂O)_n β″ and ion rich β alumina single crystals have been measured by the complex impedance method in the 25–700°C temperature range. Two mechanisms of conductivity were assumed: proton transfer at lower temperatures and H₃O⁺ diffusion in the high-temperature range. Both structures have similar properties, but ion rich β alumina possesses the best stability and the lowest activation energy (β: 0.15 eV, β″: 0.20 eV below 400 and 300°C respectively). The room-temperature conductivity is ≈5×10^?6 Ω^?1 cm^?1. The conducting properties and mechanisms are discussed and compared to other protonic or ionic conductors.     

Indication from NMR of Grotthuss mechanism for proton conduction in H2Sb4O11·nH2O

We have measured the second moment, the linewidth and the relaxation times T₁ and T₂ of the ¹H magnetic resonance signal from 4.2 to 380 K in the fact proton conductors H₂Sb₄O₁₁·nH₂O. Our results reveal that the high ionic conductivity of these materials is due to a Grotthuss-type proton diffusion mechanism with succession of molecular reorientations of H₃O⁺ ions or H₂O molecules and of proton jumps from H₃O⁺ to H₂O.     

Electrical conductivity and chemical diffusion in Perovskite-type proton conductors in H2-H2O gas mixtures

The electrical conductivities of SrZr_0.9Y_0.1O_3-δ (SZY10) and BaCe_0.95Y_0.05O_3-δ(BCY5) were measured as a function of hydrogen partial pressure P(H₂), oxygen partial pressure P(O₂), steam partial pressure P(H₂O) and temperature. Their relaxation processes were analyzed using the solution of Fick's diffusion equation to determine the chemical diffusion coefficients and surface reaction rate constants. There were the differences in chemical relaxation kinetics and the conductivity dependence on P(H₂O) between the both oxides. The chemical diffusion coefficients depend on temperature but are essentially independent of P(H₂), P(O₂) and P(H₂O). The ambipolar diffusion treatment can explain the temperature dependence of chemical diffusion coefficients quantitatively. The chemical diffusion coefficients of SZY10 is one or two order of magnitude smaller than those of BCY5 at low temperature. The sluggish conductivity relaxation in SZY10 was due to considerably small oxygen vacancy diffusion coefficients at low temperatures. The total conductivity depends on P(H₂O) in the case of SZY10, but not for BCY5. This different dependence on P(H₂O) is caused by the difference in the ratio between proton mobility and oxide-ion mobility.     

The synthesis of polycrystalline H3O+β″βAl2O3 ceramics from conventional precursor NaKβ″/βAl2O3 powders

H₃O⁺β″Al₂O₃, H₃O⁺/βAl₂O₃ and H₃O⁺β″/βAl₂O₃ /ZrO₂ ceramics of equiaxed, fine-grained microstructure were prepared by conventional synthesis techniques, gas-phase and vapour-phase ion exchange to the potassium form and field-assisted ion exchange in dilute HCl vapour to the hydronium form. The bend strength of the polycrystalline H₃O⁺β″Al₂O₃ and H₃O⁺β″/βAl₂O₃ was > 200 MPa. The conductivity of H₃O⁺β″Al₂O₃, H₃O⁺β″/βAl₂O₃ ZrO₂ was 8×10⁻⁶, 2×10⁻⁶ and 9×10⁻⁷ (Ω cm)⁻¹, respectively, at 25°C. The materials were demonstrated to perform in steam electrolysis cells at 100°C.     

Indirect Raman identification of the proton insertion in the high‐temperature [Ba/Sr][Zr/Ti]O3‐modified perovskite protonic conductors

OH⁻ and H₃O⁺ species in hydrates and simple oxides are rather well characterised from their IR, Raman and inelastic neutron points of view. For the H⁺ (H₂O) species in solid state the variability is well established and assignment remains discussed. The question of the vibrational signature of isolated proton (e.g. the ionic proton, a proton sharing its interaction with more than two acceptors) and its dynamic nature (proton gas, polaron,…) is open. H⁺‐containing modified perovskites A(Ba,Sr,…) B(Zr,Ce,Ti,…) O₃ are potential ceramic membranes for fuel cell and medium temperature water electrolysis (300–800 °C). Comparison studies of the protonated and non‐protonated lanthanide/rare earth‐modified perovskites of type Ba(Sr)Zr(Ti)O₃ as well as Al‐modified BaTiO₃ show that a broad component centred at 2500 cm⁻¹ is observed after ‘proton insertion’. Its intensity is correlated to the protonic species content as well as to the conductivity of the materials. The mixed nature of this feature is discussed: fluorescence related to the dangling bonds, A, B, C bands or new phenomena related to the ionic protons and associated electronic defect. Copyright © 2008 John Wiley & Sons, Ltd.     

Infrared study of H+(H2O)nβ″ alumina

Infrared spectra of H⁺(H₂O)_nβ″ alumina show than the dehydrated samples contain H₃O⁺ ions as dominant species while the hydrated ones consists mainly of H₃O⁺ and H₅O⁺₂ entities. Oxonium ions can occupy many different positions more or less distant form the ideal prismatic sites. This structural disorder in the conductivity plane is believed to be the main factor responsible for the high conductivity of the material.     

Electrochemical transient investigations on the diffusion of minority charge carriers in YSZ doped by transition metal oxides

The voltage relaxation of galvanic cells with zirconia based electrolytes polarised between an inert Pt electrode and a Pt/air electrode is analysed to obtain the diffusion coefficients of holes and electrons. The hole diffusion coefficient can be reduced by replacing zirconium with guest ions of different size, e.g. Nb⁵⁺ and Ti⁴⁺. The TZP phase with 3 mol% Y₂O₃ of dopant has a higher hole diffusion coefficient than the CYZ phase doped with 8 mol% Y₂O₃. 1 and 3 mol% p-type MnO_1.5 doping increases the conductivity of holes in CYZ to a large extend, but does not influence the diffusivity. This indicates that the doping increases the hole conductivity through an increased concentration of holes. In the case of 10 and 15 mol% MnO_1.5 doped Z3Y, the electronic conductivity is dominant. The chemical diffusion coefficients which are related to the oxygen vacancies were determined by GITT. The results show that the chemical diffusion coefficient of oxygen vacancies is much larger than that for holes in zirconia.     

Solvothermal synthesis and electrochemical performance of Ag-doped V6O13 as cathode material for lithium-ion battery

For the first time, belt-like V₆O₁₃ precursor was synthesized via a simple solvothermal method. Rod-like Ag-doped V₆O₁₃ was successfully synthesized by this method followed by heating at 350 °C. Both crystal domain size, electronic conductivity, and the lithium diffusion coefficient of the Ag-doped V₆O₁₃ samples are influenced by the added amount of AgNO₃. When the amount of AgNO₃ is 0.008 g, the product is rod-like particles, which are 0.1–0.3 μm wide and 1–2 μm long, and exhibits the best electrochemical performance. The enhanced electrochemical performance originates from its higher total conductivity, higher lithium diffusion coefficient, and better structural reversibility.     

Mesopore size dependence of the ionic diffusivity in alumina based composite lithium ionic conductors

Ordered-mesoporous Al₂O₃ was synthesized by a sol–gel method using neutral copolymer surfactants as structure-directing agents. The pore size was controlled over the 3–15 nm range by the use of various surfactants. Composites composed of the synthesized mesoporous Al₂O₃ and a lithium ion conductor (LiI) were prepared. The maximum dc electrical conductivity, 2.6 × 10^− 4 S cm^− 1 at 298 K, was observed for 50 LiI·50 Al₂O₃ composite with 4.2 nm average mesopore size, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which conductivity increased with decreasing pore size, except for samples with a pore size of 2.8 nm. The lithium ion diffusion coefficient determined by the ⁷Li pulsed field gradient nuclear magnetic resonance (PFG-NMR) showed excellent agreement with the measured conductivity calculated by the Nernst-Einstein equation. On the other hand, lithium migration activation energies obtained by quasielastic neutron scattering (QENS) and ⁷Li NMR spin-lattice relaxation time (T₁) were considerably smaller than those obtained from electrical conductivity and PFG-NMR. This could be explained by the ion migration mechanism in heterogeneous composites and a possible enhancement of conductivity in mesoscopically confined spaces.     

Ionic transport properties of protonic conducting solid biopolymer electrolytes based on enhanced carboxymethyl cellulose - NH<Subscript>4</Subscript>Br with glycerol

The present work investigates the ionic conductivity as well as its transport properties of carboxymethyl cellulose–NH₄Br plasticized with various weight percentage of glycerol for solid biopolymer electrolytes (SBEs) prepared by solution-casting technique. It was shown from the FTIR analysis that the complexation transpires at C=O and C–O^? from COO^? of CMC upon the addition of glycerol into the SBEs system. The highest room temperature ionic conductivity of ~10^?3 S cm^?1 was achieved at 6 wt.% of glycerol owing to the broadening in the amorphous state as demonstrated in the XRD analysis. The conductivity-temperature plots were found to be in good agreement with the conventional Arrhenius relationship. It was further shown that the conducting element is mainly due to the protonation of H⁺ where ionic mobility and diffusion coefficient was found to contribute towards the enhancement in the ionic conductivity of SBEs system.     

Hydrothermal synthesis and electrochemical performance of Mn-doped V<Subscript>6</Subscript>O<Subscript>13</Subscript> as cathode material for lithium-ion battery

Mn_xV_6?xO₁₃ (x?=?0.01, 0.02, 0.03, 0.04) were successfully synthesized via a simple hydrothermal method followed by heat-treatment. Both crystal domain size, electronic conductivity and the lithium diffusion coefficient of the Mn_xV_6?xO₁₃ samples were influenced by the doping amount of Mn²⁺. When x?=?0.02, the product was nano-sized particles and exhibited the best electrochemical performance. The enhanced electrochemical performance originated from its higher total conductivity and higher lithium diffusion coefficient.     

Investigation of H+ motion in the 21-hydrates of 12-tungstophosphoric and 12-molybdophosphoric acids by ac conductivity and pulsed 1H NMR measurements

AC conductivity and ¹H NMR relaxation time measurements are reported for the heteropolyacids H₃PM₁₂O₄₀. 21H₂O (M = W, Mo) over a range of tempereatures.Ambient temperature proton conductivites are ? 1 S m^-1, with conductivity activation energies E ? 40 kJ mol^-1.The NMR results are interpreted in terms of a range of motional processes leading to distributions of translational correlation times. The behaviour is compared to motions in zeolites and of water sorbed by charcoal.     

Proton and electron conduction in polymer intercalated vanadium pentoxide xerogel

A comprehensive proton and electron conduction in vanadium pentoxide xerogel-conducting polymer nanocomposites are analyzed by the impedance spectroscopy. The complex impedance plots are used to estimate the proton and electron conductivity. Both protonic and electronic conductivities follow Arrhenius type behavior with temperature. Protonic conductivity increases with the increase of intercalated conducting polypyrrole. The highly ordered conducting polypyrrole (PPY) molecule enhances the diffusion of H₃O⁺ ions into the host lattice. Broad dielectric loss peaks are found in a wide range of frequency domain (KHz–MHz). The intercalated water within the oxide network of vanadium pentoxide remains supercooled up to lowest measured temperature 137 K.     

Structural study and electrical properties of Zr-doped Nd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> pyrochlore compounds

Nd₂Sn₂O₇ pyrochlores with the substitution of Zr⁴⁺ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen positional parametersx = 0.331 and 0.375, while Rietveld refinements were employed for neutron diffraction data. The neutron diffraction study revealed that there are only two anion sites with 48f and 8b positions. This indicates that the 8a site, i.e. O(3) sublattice, is completely vacant and the structure is a perfect cubic pyrochlore with space group Fd3m (O _h ⁷ ). From the conductivity measurements, it is observed that the electronic conductivity dominates from room temperature up to about 525 K and forT > 525 K, the oxygen ion conduction dominates the charge transport in these compositions. Complex impedance spectroscopy indicates the existence of grain and grain boundary as two separate elements.     

Novel semiconducting iron–quinizarin metal–organic framework for application in supercapacitors*

We present conductivity data for a newly synthesised metal–organic framework FeQ, Fe(C₁₄H₆O₄).H₂O demonstrating significant electronic transport. The electrical conductivity of the material is expected to be through the π–π interaction of the ligand-quinizarin and is measured to be 1.73?×?10^?2?Scm^?1_. Its potential role as supercapacitor electrodes is discussed.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

Proton conductivity in the layer compound H3OUO2AsO4·3H2O (HU As)

The proton conductivity in H₃OUO₂AsO₄·3H₂O (HUAs) has been measured below the transition temperature at 299 K. A consistent picture of the elementary process taking place is developed from separate electrochemical, spectroscopic and calorimetric measurements. The conductivity is proposed to occur by the “vehicle mechanism” of proton transport, i.e. the cooperative motion of H₃O⁺ and H₂O. This mechanism is compared with the Grotthuss and the simple ion hopping mechanism.     

Intercalated hydrogen in yttrium barium cuprate: The state and mobility of a “Guest” and modification of the “Host” properties

The electric, magnetic, and physicochemical properties of yttrium barium hydrocuprate (H₂YBa₂Cu₃O₇) and its oxidized form (H₂YBa₂Cu₃O_7.8) are governed, to a large measure, by poorly studied behavior of hydrogen atoms in the lattice. The crystal chemical state and the mobility of a proton intercalated into yttrium barium cuprate have been investigated by the isotope exchange and inelastic neutron scattering techniques. By their behavior in the process of inelastic neutron scattering, a substantial fraction of protons can be considered mechanically free particles without chemical bonding with oxygen ions. The self-diffusion coefficient of a proton is estimated to be several orders of magnitude larger than that of oxygen ions, the latter coefficient being equal to 10^?13 cm² s^?1 at 490 K. Considerable changes in the lattice parameters and local charge distribution in the copper-oxygen subsystem are revealed by the x-ray powder diffraction analysis and nuclear quadrupole resonance (NQR). Discrete changes in the interplanar spacings along the c axis and in the Cu NQR frequencies with a gradual variation in the degrees of hydration and oxidation indicate the formation of hydrocuprate and (or) oxyhydrocuprate in the matrix of the initial material.     

Specific features of the dark conductivity in lithium niobate crystals of congruent composition

The temperature dependence of the dark conductivity in a series of doped and nominally undoped LiNbO₃ crystals of congruent composition is studied. The activation energies for the ionic and electronic contributions to the dark conductivity are determined, and the H⁺, ion diffusion coefficient is estimated. The correlation between the ionic and electronic contributions to the dark conductivity is established.