Pipe-sphere model for enhancement of ionic conductivity in composite solid electrolytes

It is well-known that the ionic conductivity of a superionic conductor when dispersed with an insulator shows a remarkable enhancement. In this work we suggest that the contribution coming from grain-boundaries and dislocations is primarily responsible for this phenomenon in a number of cases. We propose a simple theoretical model for such composites and with the aid of the Effective Medium Theory (EMT) under self-consistent scheme we estimate the effective conductivity as a function of insulator volume fraction and particle size for four composites, namely CaF₂-Al₂O₃, CuCl-Al₂O₃, Sr(NO₃)₂-Al₂O₃ and SrCl₂-Al₂O₃. This model is applicable to composites where enhancement is observed for a very low insulator volume fraction and other prevalent models are inadequate. The results exhibit a good qualitative fit to the experimental data and all characterisitic experimental observations.     

Transport in dispersed ionic conductors: Effect of insulating particle size

Dispersed ionic conductors are random mixtures of a solid salt, e.g. AgI, LiI, with fine particles of an insulating second phase, like Al₂O₃ or SiO₂. These composites can show a dramatic increase in ionic conductivity compared to the pure homogeneous system. Generally, this observation is attributed to an increased conductivity along the internal interface between the conducting salt and the insulating material. In this work a three-component random resistor network (RRN) model for dispersed ionic conductors is reviewed. In the model, the ionic conductor is represented by normally conducting bonds, the insulating material by non-conducting bonds and the interface between the two phases by highly conducting bonds. A special feature of the model is the existence of two critical concentrations of the insulating phase, p′_c and p″_c , for interface percolation and bulk conduction, respectively, where critical transport properties corresponding to conductor/superconductor and conductor/insulator networks are predicted. The model describes satisfactorily the dependence on composition of the conductivity and activation energy of dispersed ionic conductors. Furthermore, the observed effect on the conductivity of the size of dispersed particles can be described qualitatively well by a generalized version of the RRN model, which in addition predicts a sensitive dependence of the critical thresholds on particle size. Non-universality features in the critical exponents for the conductivity are also discussed within a continuum percolation analog of the model.     

Dielectric resonances in three-dimensional binary disordered media

Powdered solids often present very specific properties due to their granular nature. Such powders are often obtained by mixing two ingredients in variable proportions: conductor and insulator, or conductor and super-conductor. In a very natural way, these systems are modeled by regular lattices, whose sites or bonds are randomly chosen with given probabilities. It is known that the electrical and optical properties of random bi-dimensional (2D) networks are well described by their conductance's poles (resonances) and residues (amplitudes). The numerical implementation of a spectral method gave the spectral density, the AC conductivity, the multi-fractal properties of the moments for the local electric field (or currents), and spectrum of resonances characteristic of some small clusters (animals). This work extends the spectral method to the three-dimensional (3D) case where the problem is more complicated because the duality property and the corresponding symmetries are broken. As in the 2D-case, the two significant parameters are the ratio of the complex conductances and of both phases, and the probability p (resp. 1-p) of (resp. ). All the resonances lie on the negative real h-axis, i.e. for pure non resistive networks in the AC case. For a static (DC) system, only the value h=0 (corresponding to a binary system with finite and , or and finite) can give a resonance. Some applications are proposed, in particular the ability for small clusters (animals with one, two or three bonds) to present a singular response for well identified frequencies of the incident electromagnetic field. Received 24 March 1999     

The optimisation of mixed conduction in potential S.O.F.C. anode materials

The success of the SOFC rests heavily on materials selection. In this work we address the optimisation of mixed conductivity in fluorite compounds in the search for new improved SOFC anodes based upon oxides. The mobility of electronic carriers is considered to be much higher than that of ionic defects, therefore, doping a good ionic conductor with a small concentration of reducible transition metal ions can form promising mixed conductors. Zirconia based mixed conductors were studied for two reasons. Firstly, zirconia, stabilised in the defect fluorite structure, exhibits a high level of ionic conductivity. Secondly it is the most common electrolyte material for a S.O.F.C. An anode based on zirconia would therefore be expected to offer a good physical compatibility with the electrolyte material and to exhibit a high ionic contribution to total conductivity. Work on the system ZrO₂-Nb₂O₅-Y₂O₃ showed that the influence of composition on conduction could be determined. This enabled the optimisation of both the electronic and ionic contributions to conduction by compositional selection. These factors were extended to explain conductivity behaviour observed in the comparable system ZrO₂-TiO₂-Y₂O₃. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Phase composition, microstructure and electrical properties of alumina-zirconia eutectic composites

Oxide eutectic composites prepared by a directional solidification are noticeable for their good mechanical properties and high temperature stability in oxidizing environments. In this paper we study the influence of stabilizers (Y, Sc) on the phase composition, microstructure and electrical properties of Al₂O₃ - ZrO₂ eutectic composites. At a hypereutectic composition of the melt, we have prepared the composites with tetragonal ZrO₂, which possesses conductivities comparable to those of the composites containing cubic ZrO₂. An addition of Sc₂O₃ improves the ionic conductivity of the Al₂O₃ - (Y₂O₃)ZrO₂ eutectic composite at high temperatures. Both the microstructure and ionic conductivity do not change along the composite (grown at a constant growth rate). Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Ionic conductivity in nanoporous composites SiO2/AgI

In this work, porous silicate glasses were mixed with an ionic conductor AgI to obtain SiO₂/AgI composites. The porous glasses were either commercial Vycor glass (VPG) from Corning or synthesised from phase separated SiO₂–B₂O₃–Na₂O glasses. Depending upon the elaboration process, glasses with different pore sizes were obtained (4, 20 and 40 nm). Composites comprising different amounts of AgI were prepared by heating above the melting point of AgI. SEM characterisation of the obtained composites indicated that heat treatment induced an increase in the pore sizes. The conductivity of the composites was measured by impedance spectroscopy. The maximum conductivity, twice as large as that of pure AgI, was obtained for the 50AgI/50VPG composite, i.e. that comprising the glasses with the smallest pores.     

Numerical models for ionic conduction in CuBr-TiO2 composites and for electrolysis of CuBr films

The influence of size dispersion of CuBr grains on the experimentally observed conductivity enhancement in CuBr-TiO₂ composites is investigated. Using an extension of a random resistor network model recently introduced, we show that a bimodal size distribution can be simulated using a mean size value. Furthermore, we develop an electric breakdown model to simulate dendritic decomposition structures observed near the copper electrodes when a certain voltage is applied to thin CuBr films. Preliminary results for homogeneous systems without conductivity gradient are presented. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Dielectric resonances in disordered media

Binary disordered systems are usually obtained by mixing two ingredients in variable proportions: conductor and insulator, or conductor and super-conductor. They present very specific properties, in particular the second-order percolation phase transition, with its fractal geometry and the multi-fractal properties of the current moments. These systems are naturally modeled by regular bi-dimensional or tri-dimensional lattices, on which sites or bonds are chosen randomly with given probabilities. The two significant parameters are the ratio h = σ ₁/σ of the complex conductances, σ and σ ₁, of the two components, and their relative abundances p (or, respectively, 1 - p). In this article, we calculate the impedance of the composite by two independent methods: the so-called spectral method, which diagonalises Kirchhoff's Laws via a Green function formalism, and the Exact Numerical Renormalization method (ENR). These methods are applied to mixtures of resistors and capacitors (R-C systems), simulating e.g. ionic conductor-insulator systems, and to composites constituted of resistive inductances and capacitors (LR-C systems), representing metal inclusions in a dielectric bulk. The frequency dependent impedances of the latter composites present very intricate structures in the vicinity of the percolation threshold. In this paper, we analyse the LR-C behavior of compounds formed by the inclusion of small conducting clusters (“n-legged animals”) in a dielectric medium. We investigate in particular their absorption spectra who present a pattern of sharp lines at very specific frequencies of the incident electromagnetic field, the goal being to identify the signature of each animal. This enables us to make suggestions of how to build compounds with specific absorption or transmission properties in a given frequency domain. Received 16 August 2002 Published online 14 February 2003 RID="a" ID="a"e-mail: laurent.raymond@l2mp.fr RID="b" ID="b"e-mail: steffen.schaefer@l2mp.fr RID="c" ID="c"UMR CNRS 6137     

流体静高压下的锂离子导电性

本文改进实验方法,在0.0001—1.23GPa流体静高压下测量了整片非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃(x=0.05;0.15)及其粉末压片的离子电导率及激活体积。发现粉末压片电导率峰值是由非晶微粒间的接触电导及非晶微粒体电导两者叠加;对整片非晶电导率的压力效应用离子迁移通道的物理图象给出初步的微观解释。此外,还观测到氧化铝组分减少使电导率的压力转变点明显降低;测量出不同温度热处理以及300℃等温热处理4—20h后离子电导率-压力曲线的变化规律,仍可归因于非晶态相分离及两种非晶相的先后晶化。 关键词：     

Preparation of dense La<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>Ga<Subscript>0.8</Subscript>Mg<Subscript>0.2</Subscript>O<Subscript>3-δ</Subscript> with high ionic conductivity by solid-state synthesis

The results of a systematic investigation on the effects of processing steps, via solid-state reactions, on structural phase characteristics and ionic conductivity of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ solid electrolyte are reported. The main purpose of this work is to establish an optimized route for obtaining good densification and high ionic conductivity of this solid electrolyte. Processing routes with three successive calcinations at 1250 °C followed by attrition milling (R1), and with two sequences of calcination at 1350 °C with intermediary attrition milling (R2) give rise to near full density at 1450 °C sintering temperature. The rate of grain growth is fast when the relative density reaches 95%. Elemental mapping reveals uniform distribution of the constituents in the matrix along with La₄Ga₂O₉, LaSrGa₃O₇ and sub-micrometer MgO grains at grain boundaries. The ionic conductivity of grains remains unchanged with the processing route and sintering profile. The blocking effect of charge carriers at grain boundaries decreases with increasing the dwell temperature.     

晶态-非晶态复合锂离子导体的电学性质

本文研究了晶态LiCl-非晶态Li₂O·3B₂O₃复合锂离子导体的电学性质。实验发现这种晶态-非晶态新型复合离子导体的电学性质变化具有新的现象,即在宏观电导率σ_m-组成曲线上出现了电导率增加的“双峰”效应。相应地,在表观活化能E_m-组成曲线和介电常数ε_m-组成曲线上出现了“双谷”。本文还详细讨论了这些实验现象,得到了与理论相符合的结果。 关键词：     

用正电子湮没方法研究快离子导体

本文用正电子湮没方法研究了作为快离子导体的LiF-LiCl-B₂O₃,LiF-B₂O₃新体系。发现正电子湮没的中间成分的强度I₂与材料的电导率logσ之间有直线关系。配合湮没线形参数的测定结果,表明在微晶态三元体系LiF-LiCl-B₂O₃中,微晶与网络之间的晶界空位为锂离子传导提供了更多的导电通道,致使这类材料具有更好的导电性。 关键词：     

Electrical transport properties of gadolinium scandium gallium garnet

Electrical conductivity and thermoelectric power are measured on a single crystal of Gd_3.0Sc_1.8Ga_3.2O₁₂ (GSGG) between 1273 and 1673 K. The measurements are made both in air and in controlled atmospheres, and P_O2 varies from 10^?1.68 to 10^?5.6 MPa. The data indicate GSGG may well be a mixed conductor in this temperature and P_O2 range, with n-type electronic conductivity and ionic transport on the oxygen sublattice. Changes in temperature induce long-lived disequilibrium in electrical conductivity of GSGG (over 30 h at T < 1373 K) that can be explained by temperature dependent cation redistribution. The effective activation energy for equilibrium electrical conductivity is E_a = 2.40 ± 0.05 eV, as opposed to values of E_a between 1.8 and 2.2 eV during actual temperature changes. An additional contribution in the equilibrium E_a, due to thermally activated cation redistribution, can account for the higher value seen.     

AgI(Cr2O3)混合离子导体改性的机理研究

本文研究了Agl(Cr₂O₃)混合离子导体的红外吸收光谱、近紫外、可见反射光谱,透射电子显微镜的显微形貌及成份分析,发现混合离子导体的微观结构与纯Agl,Cr₂O₃不同。由透射电子显微镜的显微形貌得出不同于他人的介质模型。提出电介质引起的变形极化,导致了微观精细结构改变的观点。并对其物性改变的机理给予了讨论。 关键词：     

Structure property correlation in lithium borophosphate glasses

To investigate the influence of cation mobility variation due to the mixed glass former effect, 0.45Li₂O-(0.55 − x) P₂O₅−x B₂O₃ glasses (0 ≤; x ≤ 0.55) are studied keeping the molar ratio of Li₂O/(P₂O₅ + B₂O₃) constant. Addition of B₂O₃ into lithium phosphate glasses increases the glass transition temperature (T _g) and number density, decreases the molar volume, and generally renders the glasses more fragile. The glass system has been characterised experimentally by XRD, XPS and impedance studies and studied computationally by constant volume molecular dynamics (MD) simulations and bond valence (BV) method to identify the structural variation with increasing the B₂O₃ content, its consequence for Li⁺ ion mobility, as well as the distribution of bridging and non-bridging oxygen atoms. These studies indicate the increase of P-O-B bonds (up to Y = [B₂O₃]/([B₂O₃] + [P₂O₅]) ≈ 0.5 and B-O-B bonds, as well as the decrease of P-O-P bonds and non-bridging oxygens (NBOs) with rising B₂O₃ content. The system with Y ≈ 0.5 exhibits maximum ionic conductivity, 1.0 × 10⁻⁷ S cm⁻¹, with activation energy 0.63 V. Findings are rationalised by a model of structure evolution with varying B₂O₃ content Y and an empirical model quantifying the effect of the various structural building blocks on the ionic conductivity in this mixed glass former system.     

Rate of creation of the contacts between grains in a loose array of particles submitted to an uniaxial pressure

Macroscopic resistivity measurements have been performed on TiC/Al₂O₃ random mixtures submitted to uniaxial compression (0-95 kN). Such a random mixture exhibits an insulator-conductor transition which appears at increasing force while decreasing the conductive composition of the TiC/Al₂O₃ mixture. It is demonstrated that the conductivity behavior may be understood in the framework of a site percolation model. Finally, the rate of creation of the contacts between conductive grains is extracted from the macroscopic resistivity measurements. Received 6 December 2000 and Received in final form 30 March 2001     

Structural, thermal, and conductivity studies of high molecular weight poly(vinylchloride)-lithium triflate polymer electrolyte plasticized by dibutyl phthalate

Poly(vinylchloride) (PVC) is an insulator and acts as a host in polymer electrolyte systems where addition of inorganic salt lithium trifluoromethanesulfonate (LiCF₃SO₃) and dibutyl phthalate (DBP) converts the system to become conductor. The conductivity of polymer electrolytes is explained on the basis of ionic mobility. Thirty-five weight percent DBP plasticized polymer electrolyte has the highest conductivity value (3.30?×?10^?9 S cm^?1) at 303 K. Temperature dependence of the conductivity of polymer films obeys the Arrhenius rule. X-ray diffraction (XRD) proves that addition of DBP will increase the amorphous nature of the system and lead to enhancement in ionic conductivity. Complexation between high molecular weight PVC, LiCF₃SO₃, and DBP is confirmed by the shifting of peaks, decreasing of peaks intensity, and broadening of peaks in XRD. Thermogravimetric analysis reveals that addition of DBP to PVC–LiCF₃SO₃ system reduces the stability of the film. Subsequently, thermal stability decreases with the increase in DBP content in the polymer electrolytes.     

Preparation of Co3O4 nanoplate/graphene sheet composites and their synergistic electrochemical performance

Co₃O₄ nanoplate/graphene sheet composites were prepared through a two-step synthetic method. The composite material as prepared was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The platelet-like morphology of Co₃O₄ leads to a layer-by-layer-assembled structure of the composites and a good dispersion of Co₃O₄ nanoplates on the surface of graphene sheets. The electrochemical characteristics indicate that the specific capacitance of the composites is 337.8 F?g^?1 in comparison with the specific capacitance of 204.4 F?g^?1 without graphene sheets. Meanwhile, the composites have an excellent rate capability and cycle performance. The results show that the unique microstructure of the composites enhances the electrochemical capacitive performance of Co₃O₄ nanoplates due to the three-dimensional network of graphene sheets for electron transport increasing electric conductivity of the electrode and providing unobstructed pathways for ionic transport during the electrochemical reaction.     

Influence of Bi<Superscript>3+</Superscript> ions on low temperature D.C. conductivity of Na<Subscript>2</Subscript>SiCuO<Subscript>4</Subscript> glasses

Sodium silicate glasses doped with CuO and mixed with different contents of Bi₂O₃ (ranging from 4 to 16 mol%) were prepared. D.C. conductivity studies over a range of temperature from 225 to 325 K have been carried out. The conductivity is observed to decrease linearly with increase of Bi₂O₃ concentration. The results are analyzed using optical absorption, ESR, and IR spectral data. The spectroscopic studies have indicated that there is a gradual reduction divalent copper ions to monovalent ions with increase of Bi₂O₃ concentration. These studies have also indicated that such Cu⁺ ions participate in the glasses network forming and increase the polymerization of the glass network. The analysis of the results of D.C. conductivity indicated that in temperature region T > θ _D/2, the small polaron hoping model is valid, and the conduction is predicted to be adiabatic type. The analysis of the results has further revealed that there is a gradual change over of conduction mechanism from ionic to electronic with increase of Bi₂O₃ concentration. The low temperature part of D.C. conductivity is explained using variable range hopping (VRH) model.     

非晶态离子导体Li2B2O4的核磁共振研究

本文报道了非晶态离子导体Li₂B₂O₄的⁷Li核磁共振研究。测量了⁷Li核磁共振谱与温度的关系。实验中发现,Li₂B₂O₄的晶态、非晶态和部分晶化样品的⁷Li核磁共振谱有很大的不同,且在部分晶化样品的⁷Li核磁共振谱上有附加的小峰,它与LiCl(Al₂O₃)的⁷Li核磁共振谱上附加的小峰相类似。我们也对非晶态离子导体B₂O₃-0.7Li₂O-0.7LiCl进行了⁷Li核磁共振研究,其结果与上面的类似。研究结果表明,它们都起因于非晶母体与微晶的界面效应。 关键词：