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At least 757 records · Page 42

Synthesis and Characterization of Li4Ti5O12 Anode Materials with Enhanced High-Rate Performance in Lithium-Ion Batteries

ABSTRACT Li 4 Ti 5 O 12 (LTO) represents a promising anode material for lithium ion batteries, however, it suffers from limitations associated with poor intrinsic electron conductivity as well as moderate ionic conductivity. Hence, to achieve the goal of creating LTO anodes with improved high-rate performance, we have put forth a number of targeted fundamental strategies. Herein we discuss the roles of controllably tuning (i) morphology, (ii) attachment modalities of carbon, and (iii) ion doping of the LTO material. In addition, we also demonstrated in situ studies of lithiation-driven structural transformations in LTO via a combination of X-ray absorption spectroscopy and ab initio calculations, which have been proven to be powerful tools to probe the negligible volume change and extraordinary stability of LTO upon repeated charge/discharge cycles.

energy storage (including batteries and capacitors↗

Double-membrane triple-electrolyte redox flow battery design

A redox flow battery is provided having a double-membrane (one cation exchange membrane and one anion exchange membrane), triple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and one electrolyte positioned between and in contact with the two membranes). The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte. This design physically isolates, but ionically connects, the negative electrolyte and positive electrolyte. The physical isolation offers great freedom in choosing redox pairs in the negative electrolyte and positive electrolyte, making high voltage of redox flow batteries possible. The ionic conduction drastically reduces the overall ionic crossover between negative electrolyte and positive one, leading to high columbic efficiency.

25 ENERGY STORAGE↗

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

Systems and methods of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In2O3 films grown on ionically conducting Y2O3-stabilized ZrO2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygen vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behavior is dependent on interface properties and is attained without cation doping or changes in the gas environment in contact with the sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanostructured Crystals of Fluorite Phases Sr{sub 1–x}R{sub x}F{sub 2+x} and Their Ordering: 12. Influence of Structural Ordering on the Fluorine-Ion Conductivity of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} Alloys (R = Tb or Tm) at Their Annealing

The ionic conductivity of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} alloys (rational Sr{sub 2}RF{sub 7} compositions) in SrF{sub 2}–RF{sub 3} systems (R = Tb or Tm), prepared by spontaneous crystallization, has been investigated for the “as-grown” state and after annealing in CF{sub 4} at 900 ± 20°C for 96 h. As-grown samples of both compositions, prepared by fast (200°C/min) melt crystallization, exhibit partial (nonequilibrium) ordering, which increases from Tb to Tm. Annealing of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} alloys yields strong ordering (equilibrium for the annealing temperatures) of the fluorite structure (CaF{sub 2} type, sp. gr. Fm3̅m, Z = 4) at the formation of t-Sr{sub 2}RF{sub 7} tetragonal compound (sp. gr. I4/m, Z = 30). It is established that ordering of the alloy fluorite structure reduces the fluorine-ion conductivity. After the annealing, the conductivity of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} alloys with the initial (nonequilibrium) ordering stage of t-Sr{sub 2}RF{sub 7} phases with almost complete (equilibrium) ordering decreases by a factor of 3–4.5.

36 MATERIALS SCIENCE↗

Interface modulated currents in periodically proton exchanged Mg doped lithium niobate

Conductivity in Mg doped lithium niobate (Mg:LN) plays a key role in the reduction of photorefraction and is therefore widely exploited in optical devices. However, charge transport through Mg:LN and across interfaces such as electrodes also yields potential electronic applications in devices with switchable conductivity states. Furthermore, the introduction of proton exchanged (PE) phases in Mg:LN enhances ionic conductivity, thus providing tailorability of conduction mechanisms and functionality dependent on sample composition. To facilitate the construction and design of such multifunctional electronic devices based on periodically PE Mg:LN or similar ferroelectric semiconductors, fundamental understanding of charge transport in these materials, as well as the impact of internal and external interfaces, is essential. In order to gain insight into polarization and interface dependent conductivity due to band bending, UV illumination, and chemical reactivity, wedge shaped samples consisting of polar oriented Mg:LN and PE phases were investigated using conductive atomic force microscopy. In Mg:LN, three conductivity states (on/off/transient) were observed under UV illumination, controllable by the polarity of the sample and the externally applied electric field. Measurements of currents originating from electrochemical reactions at the metal electrode–PE phase interfaces demonstrate a memresistive and rectifying capability of the PE phase. Furthermore, internal interfaces such as domain walls and Mg:LN–PE phase boundaries were found to play a major role in the accumulation of charge carriers due to polarization gradients, which can lead to increased currents. The insight gained from these findings yield the potential for multifunctional applications such as switchable UV sensitive micro- and nanoelectronic devices and bistable memristors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Self-regulating surface chemistry for more robust highly durable solid oxide fuel cell cathodes

In this project we explored the possibility of mitigating silicon poisoning of Pr doped ceria (PCO) electrodes for oxygen reduction in SOFC. The approach was to dope PCO with various amount of lanthanum and study the new compositions in terms of their mixed conduction properties, their oxygen surface exchange kinetics, as well as their resistance to silicon poisoning. The effects of lanthanum doping on the transport properties and oxygen exchange kinetics of La x (Ce 0.9 Pr 0.1 ) 1-x O 2-δ (x=0, 0.1 and 0.2) have been investigated by electrical conductivity on bulk samples and optical relaxation on thin films respectively. Lanthanum substitution was observed to increase the magnitude of ionic conductivity to values comparable to that of single substituted La x Ce 1-x O 2-δ , with a maximum for a La content of x = 0.1, reaching σ = 9.5×10 -3 S·cm -1 at 600 °C and a decrease in activation energy from ≈ 1 eV for Ce 0.9 Pr 0.1 O 2-δ down to ≈ 0.75 eV for the lanthanum substituted compositions. At the same time, a significant electronic contribution to the total conductivity, estimated to be on the order of 10%, supports significant mixed ionic-electronic conductivity.

08 HYDROGEN↗

Conductance of Ion Channels - Theory vs. Experiment

Transmembrane ion channels mediate a number of essential physiological processes in a cell ranging from regulating osmotic pressure to transmission of neural signals. Kinetics and selectivity of ion transport is of critical importance to a cell and, not surprisingly, it is a subject of numerous experimental and theoretical studies. In this presentation we will analyze in detail computer simulations of two simple channels from fungi - antiamoebin and trichotoxin. Each of these channels is made of an alpha-helical bundle of small, nongenomically synthesized peptides containing a number of rare amino acids and exhibits strong antimicrobial activity. We will focus on calculating ionic conductance defined as the ratio of ionic current through the channel to applied voltage. From molecular dynamics simulations, conductance can be calculated in at least two ways, each involving different approximations. Specifically, the current, given as the number of charges transferred through the channel per unit of time, can be obtained from the number of events in which ions cross the channel during the simulation. This method works well for large currents (high conductance values and/or applied voltages). If the number of crossing events is small, reliable estimates of current are difficult to achieve. Alternatively, conductance can be estimated assuming that ion transport can be well approximated as diffusion in the external potential given by the free energy profile. Then, the current can be calculated by solving the one-dimensional diffusion equation in this external potential and applied voltage (the generalized Nernst-Planck equation). To do so three ingredients are needed: the free energy profile, the position-dependent diffusion coefficient and the diffusive flux of ions into the channel. All these quantities can be obtained from molecular dynamics simulations. An important advantage of this method is that it can be used equally well to estimating large and small currents. In addition, once the free energy profile becomes available the full current-voltage dependence can be readily obtained. For both channels we carried out calculations using both approaches. We also tested the main assumptions underlying the diffusive model, such as uncorrelated nature of individual crossing events and Fickian diffusion. The accuracy and consistency of different methods will be discussed. Finally we will discuss how comparisons between calculated and measured ionic conductance and selectivity of transport can be used for determining structural models of the channels.

Pohorille, Andrew↗

Exploring the Role of Humidity, Temperature, and Mixed Ionic and Electronic Conductivity on SOFC Anode Electrocatalysis

Infiltration of nanoscale electrocatalysts into Ni/yttria-stabilized zirconia (Ni-YSZ) cermets has been shown to improve the electrochemical performance of solid oxide fuel cell (SOFC) anodes. While infiltrated electrodes in SOFCs result in improved cell performance, long-term operation leads to coarsening of the infiltrated nanoparticles and negates the short-term performance improvements. This study explores the roles of humidity, temperature, and number of cycles of nanocatalyst infiltration in improving mixed conduction within the Ni-YSZ electrode. Two mixed conduction phases were studied: Gd 0.1 Ce 0.9 O 2-δ (GDC) as an infiltrant into Ni-YSZ electrodes, and Ni/transition metal doped-YSZ electrodes infiltrated with Ni. Analysis of impedance data from these cells shows improved electrochemical performance in infiltrated cells with mixed conduction compared with infiltrated cells containing purely ionic and electronic conducting phases. Improved anode performance is attributed to the availability of electronic pathways through predominantly ionic-conducting phases to connect distant Ni nanoparticles and/or Ni grains.

25 ENERGY STORAGE↗

Thermoelectric properties and impedance spectroscopy of polycrystalline samples of the beta-gallia rutile intergrowth, (Ga,In){sub 4}(Sn,Ti){sub 5}O{sub 16}

Polycrystalline samples of Ga{sub 3}In(Sn{sub 1-y}Ti{sub y}){sub 5}O{sub 16}, y{<=}0.3 were prepared by solid-state synthesis and characterized to determine their optical properties, thermoelectric properties and electrical impedance. Using diffuse reflectance data and assuming a direct band gap, the band gap of the material ranges from 3.58 eV for y=0 to 3.74 eV for y=0.2. The dc conductivity decreased with increasing Ti content and was thermally activated, ranging from {<=}10{sup -5} S/cm at 300 Degree-Sign C to 0.03 S/cm at 1000 Degree-Sign C for Ga{sub 3}InSn{sub 5}O{sub 16}. The Seebeck coefficient was negative indicating n-type conduction. The activation energies for dc conduction and thermopower were similar, ranging from 1.4{+-}0.1 eV for y=0 to 1.8{+-}0.2 eV for y=0.2, suggesting band conduction. The thermal conductivity of Ga{sub 3}InSn{sub 5}O{sub 16} ranged from 1.1 W/m K at 500 {sup o}C to 0.75 W/m K at 800 Degree-Sign C. The highest figure of merit measured was 2 Multiplication-Sign 10{sup -4} at {approx}900 Degree-Sign C, which is much lower than desired for thermoelectric materials. A comparison of dc conductivity and impedance data indicated a substantial ionic contribution for samples containing titanium. - Graphical abstract: The thermoelectric properties of polycrystalline Ga{sub 3}In(Sn{sub 1-y}Ti{sub y}){sub 5}O{sub 16}, y{<=}0.3 were measured in air at 300-900 Degree-Sign C. The materials are broad-band n-type semiconductors with non-negligible ionic conduction for samples prepared with y>0. The thermoelectric figure of merit is much lower than desired for practical thermoelectric devices. Highlights: Black-Right-Pointing-Pointer Ga{sub 3}In(Sn{sub 1-y}Ti{sub y}){sub 5}O{sub 16}, y{<=}0.2 is a broad-band n-type semiconductor. Black-Right-Pointing-Pointer The conductivity of Ti-containing samples show evidence of an ionic as well as an electronic contribution. Black-Right-Pointing-Pointer The thermal conductivity of polycrystalline Ga{sub 3}In(Sn{sub 1-y}Ti{sub y}){sub 5}O{sub 16} decreases with increasing temperature. Black-Right-Pointing-Pointer The thermoelectric figure of merit for Ga{sub 3}In(Sn{sub 1-y}Ti{sub y}){sub 5}O{sub 16} is lower than desired for practical thermoelectric devices.

36 MATERIALS SCIENCE↗

Surface Reconstruction Limited Conductivity in Block-Copolymer Li Battery Electrolytes

Solid polymer electrolytes for lithium batteries promise improvements in safety and energy density if their conductivity can be increased. Nanostructured block-copolymer electrolytes specifically have the potential to provide both good ionic conductivity and good mechanical properties. This study shows that the previously neglected nanoscale composition of the polymer electrolyte close to the electrode surface has an important effect on impedance measurements, despite its negligible extent compared to the bulk electrolyte. Using standard stainless steel blocking electrodes, the impedance of lithium salt-doped poly(isoprene-b-styrene-b-ethylene oxide) (ISO) exhibits a marked decrease upon thermal processing of the electrolyte. In contrast, covering the electrode surface with a low molecular weight poly(ethylene oxide) (PEO) brush results in higher and more reproducible conductivity values, which are insensitive to the thermal history of the device. A qualitative model of this effect is based on the hypothesis that ISO surface reconstruction at the different electrode surfaces leads to a change in the electrostatic double layer, affecting electrochemical impedance spectroscopy measurements. As a main result, PEO-brush modification of electrode surfaces is beneficial for the robust electrolyte performance of PEO-containing block-copolymers and may be crucial for their accurate characterization and use in Li-ion batteries.

block-copolymer electrolytes↗

Cu{sub 22}Bi{sub 12}S{sub 21}Cl{sub 16}-A mixed conductor with fast one-dimensional copper(I) ion transport

Melting reactions of Cu, CuCl, S, and Bi{sub 2}S{sub 3} yield black, shiny needles of Cu{sub 22(1)}Bi{sub 12}S{sub 21(1)}Cl{sub 16(1)}. The compound decomposes peritectically at 649(5) K. Oxidation state +I of the copper atoms is supported by Cu-K-XANES. The compound crystallizes in the hexagonal space group P6/m with a=2116.7(7) pm and c=395.17(5) pm. Seven anions coordinate each of the two independent bismuth cations in the shape of mono-capped trigonal prisms. These polyhedra share edges and faces to form trigonal and hexagonal tubes running along [0 0 1]. The hexagonal tubes are centered by chloride ions, which are surrounded by disordered copper cations. The majority of copper cations are distributed over numerous sites between the tubes. The Joint Probability Density Function (JPDF) reveals a continuous pathway along [0 0 1]. The high mobility of the copper cations along [0 0 1] was demonstrated by impedance spectroscopy and DC polarization measurements on single crystals. The ionic conductivity at 450 K is about {sigma}{sub ion}=0.06 S cm{sup -1}, and the activation energy for Cu{sup +} ion conduction is E{sub a}=0.44 eV. The chemical diffusion coefficient of copper is in the order of D{sub cu}{sup {delta}=}10{sup 19} cm{sup -3} at 420 K. The electronic band gap (p-type conductor) was determined as E{sub g}=0.06 eV. At room temperature the thermal conductivity of a pressed pellet is about {kappa}=0.3 W K{sup -1} m{sup -1} and the Seebeck coefficient is S=43 {mu}V K{sup -1}. -- Graphical Abstract: Copper cations easily move through the rigid tubular crystal structure of Cu{sub 22}Bi{sub 12}S{sub 21}Cl{sub 16}. Display Omitted

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and conductivity studies of Y{sub 10-x}La{sub x}W{sub 2}O{sub 21}

The aim of this work was to determine structural parameters of the Y{sub 10-x}La{sub x}W{sub 2}O{sub 21} (x=0-10) solid solution series and investigate their electric properties. Crystallographic data shows a gradual increase in symmetry with increasing La content, as the structure evolves from orthorhombic, Y{sub 10}W{sub 2}O{sub 21}, towards the pseudo-cubic structure of Y{sub 5}La{sub 5}W{sub 2}O{sub 21}. The solubility limit of La{sub 2}O{sub 3} was found to be 50% (x=5). Above this level two phases were observed, La{sub 6}W{sub 2}O{sub 15} and (La,Y){sub 10+x}W{sub 2-x}O{sub 21-{delta}}. The conductivity of Y rich samples was very low, with sigma of the order 2x10{sup -5}-5x10{sup -5} S cm{sup -1} at 1000 deg. C, whilst ionic conductivity was observed for most La rich doped samples. The highest conductivity was observed for La{sub 10}W{sub 2}O{sub 21} and its doped analogues, at 1x10{sup -3}-5x10{sup -3} S cm{sup -1} at 1000 deg. C. Unit cell parameters were determined as a function of temperature from 0 to 1000deg. C, and thermal expansion of these materials was determined from temperature studies carried out at the Australian Synchrotron facility in Melbourne, Victoria, Australia. - Graphical abstract: The solubility limit of La{sub 2}O{sub 3} in Y{sub 10}W{sub 2}O{sub 21} was found to be >50% after which the structure was found to change to Weberite type structure, A' A''B' B''O{sub 7} that is closely related to the pyrochlore.

36 MATERIALS SCIENCE↗

Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors

Abstract Conjugated polymers that support mixed (electronic and ionic) conduction are in demand for applications spanning from bioelectronics to energy harvesting and storage. To design polymer mixed conductors for high‐performance electrochemical devices, relationships between the chemical structure, charge transport, and morphology must be established. A polymer series bearing the same p‐type conjugated backbone with increasing percentage of hydrophilic, ethylene glycol side chains is synthesized, and their performance in aqueous electrolyte gated organic electrochemical transistors (OECTs) is studied. By using device physics principles and electrochemical analyses, a direct relationship is found between the OECT performance and the balanced mixed conduction. While hydrophilic side chains are required to facilitate ion transport—thus enabling OECT operation—swelling of the polymer is not de facto beneficial for balancing mixed conduction. It is shown that heterogeneous water uptake disrupts the electronic conductivity of the film, leading to OECTs with lower transconductance and slower response times. The combination of in situ electrochemical and structural techniques shown here contributes to the establishment of the structure–property relations necessary to improve the performance of polymer mixed conductors and subsequently of OECTs.

Savva, Achilleas↗

Consequences of Ca multisite occupation for the conducting properties of BaTiO{sub 3}

In combination with the dielectric modulus formalism and theoretical calculations, a newly developed defect incorporation mode, which is a combination of the standard A- and B-site doping mechanisms, is used to explain the conducting properties in 5 mol% Ca-doped BaTiO{sub 3}. Simulation results for Ca solution energies in the BaTiO{sub 3} lattice show that the new oxygen vacancy inducing mixed mode exhibits low defect energies. A reduction in dc conductivity compared with undoped BaTiO{sub 3} is witnessed for the incorporation of Ca. The conducting properties of 5 mol% Ca-doped BaTiO{sub 3} are analyzed using molecular dynamics and impedance spectroscopy. The ionic conductivity activation energies for each incorporation mode are calculated and good agreement with experimental data for oxygen migration is observed. The likely existence of the proposed defect configuration is also analyzed on the basis of these methods. - Graphical abstract: Oxygen vacancy formation as a result of self-compensation in Ca-doped BaTiO{sub 3}.

36 MATERIALS SCIENCE↗

On the molecular correlations that result in field-dependent conductivities in electrolyte solutions

Employing recent advances in response theory and nonequilibrium ensemble reweighting, we study the dynamic and static correlations that give rise to an electric field-dependent ionic conductivity in electrolyte solutions. We consider solutions modeled with both implicit and explicit solvents, with different dielectric properties, and at multiple concentrations. Implicit solvent models at low concentrations and small dielectric constants exhibit strongly field-dependent conductivities. We compare these results to Onsager-Wilson theory of the Wien effect, which provides a qualitatively consistent prediction at low concentrations and high static dielectric constants but is inconsistent away from these regimes. The origin of the discrepancy is found to be increased ion correlations under these conditions. Explicit solvent effects act to suppress nonlinear responses, yielding a weakly field-dependent conductivity over the range of physically realizable field strengths. By decomposing the relevant time correlation functions, we find that the insensitivity of the conductivity to the field results from the persistent frictional forces on the ions from the solvent. Our findings illustrate the utility of nonequilibrium response theory in rationalizing nonlinear transport behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Ceramic Interconnect Materials for SOFC

Currently, acceptor-doped lanthanum chromite is the state-of-the-art ceramic interconnect material for high temperature solid oxide fuel cells (SOFCs) due to its fairly good electronic conductivity and chemical stability in both oxidizing and reducing atmospheres, and thermal compatibility with other cell components. The major challenge for acceptor-doped lanthanum chromite for SOFC interconnect applications is its inferior sintering behavior in air, which has been attributed to the development of a thin layer of Cr2O3 at the interparticle necks during the initial stages of sintering. In addition, lanthanum chromite is reactive with YSZ electrolyte at high temperatures, forming a highly resistive lanthanum zirconate phase (La2Zr2O7), which further complicates co-firing processes. Acceptor-doped yttrium chromite is considered to be one of the promising alternatives to acceptor-doped lanthanum chromite because it is more stable with respect to the formation of hydroxides in SOFC operating conditions, and the formation of impurity phases can be effectively avoided at co-firing temperatures. In addition, calcium-doped yttrium chromite exhibits higher mechanical strength than lanthanum chromite-based materials. The major drawback of yttrium chromite is considered to be its lower electrical conductivity than lanthanum chromite. The properties of yttrium chromites could possibly be improved and optimized by partial substitution of chromium with various transition metals. During FY10, PNNL investigated the effect of various transition metal doping on chemical stability, sintering and thermal expansion behavior, microstructure, electronic and ionic conductivity, and chemical compatibility with other cell components to develop the optimized ceramic interconnect material.

30 DIRECT ENERGY CONVERSION↗

Electrolytes - Technology review

Safety, lifetime, energy density, and costs are the key factors for battery development. This generates the need for improved cell chemistries and new, advanced battery materials. The components of an electrolyte are the solvent, in which a conducting salt and additives are dissolved. Each of them plays a specific role in the overall mechanism of a cell: the solvent provides the host medium for ionic conductivity, which originates in the conductive salt. Furthermore, additives can be used to optimize safety, performance, and cyclability. By understanding the tasks of the individual components and their optimum conditions of operation, the functionality of cells can be improved from a holistic point of view. This paper will present the most important technological features and requirements for electrolytes in lithium-ion batteries. The state-of-the-art chemistry of each component is presented, as well as different approaches for their modification. Finally, a comparison of Li-cells with lithium-based technologies currently under development is conducted.

25 ENERGY STORAGE↗

High temperature crystal structures and superionic properties of SrCl{sub 2}, SrBr{sub 2}, BaCl{sub 2} and BaBr{sub 2}

The structural properties of the binary alkaline-earth halides SrCl{sub 2}, SrBr{sub 2}, BaCl{sub 2} and BaBr{sub 2} have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl{sub 2} undergoes a gradual transition to a superionic phase at 900-1100 K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3) K, the tetragonal phase of SrBr{sub 2} undergoes a first-order transition to a cubic fluorite phase. This high temperature phase shows the presence of extensive disorder within the anion sublattice, which differs from that found in superionic SrCl{sub 2}. BaCl{sub 2} and BaBr{sub 2} both adopt the cotunnite crystal structure under ambient conditions. BaCl{sub 2} undergoes a first-order structural transition at 917(5) K to a disordered fluorite-structured phase. The relationship between the (disordered) crystal structures and the ionic conductivity behaviour is discussed and the influence of the size of the mobile anion on the superionic behaviour is explored. - Graphical abstract: Anomalous behaviour of the lattice expansion of SrCl{sub 2} at temperatures of {approx}1000 K is associated with the gradual transition to a superionic phase, whilst SrBr{sub 2} undergoes a first-order structural transition ({beta}{yields}{alpha}) to a fluorite-structured superionic phase at 920(3) K. Highlights: > Anomalous behaviour of the lattice expansion of SrCl{sub 2} occurs at temperatures {approx}1000 K. > Crystal structure of {beta}-SrBr{sub 2} is described in detail. > On heating, SrBr{sub 2} and BaCl{sub 2} transform to a fluorite-structured superionic phase. > Temperature dependence of the BaCl{sub 2} and BaBr{sub 2} structures is presented. > Nature of the superionic phases within the alkaline-earth halides is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗