Preparation, structure and oxide ion conductivity in Ce6-xYxMoO15-delta (x=0.1-1.4) solid solutions

The Ce6-xYxMoO15-delta solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce5.5Y0.5MoO15-delta ranging from 5.9 X 10(-5)(S cm(-1)) at 300 degrees C to 1.3 X 10(-2)(S cm(-1)) at 650 degrees C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 degrees C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.

The relation between molecular motion and ion conductivity on a new comblike polymer

A new amorphous comblike polymer(CBP) based on methylvinyl ether/maleic anhydride alternating copolymer backbone and on oligooxyethylene side chain was synthesized The dynamic mechanical properties of CBP-Li salt complexes showed that there were two glass transitions. There are two peaks in the plot of the ionic conductivity vs. Li salt concentration. The plot of Log sigma against 1/(T-To) shows an unusual dual VTF behavior when using sidechain glass transition temperature (T-beta) as To.

Ion conductivity in amorphous polymer/salt mixtures

Amorphous polymer/salt mixtures based on polyvinyl alcohol and poly(hydroxyethylacrylate) and poly(hydroxyethylmethacrylate) are described. The polyvinylalcohol materials have been prepared by a solvent free hot pressing technique as well as the traditional solvent casting method. The hot pressing technique allows the production of samples which are genuinely free of solvents and thereby has allowed an assessment in this work of the effect of residual solvent on conductivity. The acrylate materials were prepared by direct polymerization of monomer/salt mixtures, thus avoiding the need for solvents. These materials have glass transitions around or well above room temperature, but nonetheless have conductivities as high as 10⁻⁷ S/cm at room temperature. The temperature and composition dependence of conductivity are also presented.

Surprising effect of nanoparticle inclusion on ion conductivity in a lithium doped organic ionic plastic crystal

Doping lithium bis(trifluoromethanesulfonyl)amide (Li[NTf₂]) into the N-ethyl,N′-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ([C₂mpyr][NTf₂]) plastic crystal material has previously indicated order of magnitude enhancements in ion transport and conductivity over pure [C₂mpyr][NTf₂]. Recently, conductivity enhancements in this ionic plastic crystal induced by SiO₂ nanoparticles have also been reported. In this work the inclusion of SiO₂ nanoparticles in Li ion doped [C₂mpyr][NTf₂] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, positron annihilation lifetime spectroscopy (PALS), Raman spectroscopy, NMR spectroscopy and scanning electron microscopy (SEM). Solid state ¹H NMR indicates that the addition of the nanoparticles increases the mobility of the [C₂mpyr] cation and positron lifetime spectroscopy (PALS) measurements indicate an increase in mean defect size and defect concentration as a result of nanoparticle inclusion, especially with 10 wt% SiO₂. Thus, the substantial drop in ion conductivity observed for this doped nanocomposite material was surprising. This decrease is most likely due to the decrease in mobility of the [NTf₂] anion, possibly by its adsorption at the SiO₂/grain boundary interface and concomitant decrease in mobility of the Li ion.

High conductivity molten salts based on the imide ion

The bis(trifluoromethanesulfonyl)imide ion has recently been used in its lithium salt as a useful ion in solid polymer electrolytes because of the reduced degree of ion interaction its diffuse charge generates. In this work we have synthesised a number of novel salts based on the ammonium and pyrrolidinium cations of this anion. The salts all show reduced melting points compared with analogous halide salts. In some cases they are molten at room temperature. This latter group of salts have been characterized with respect to their properties as ionic liquids; the highest room temperature conductivity 2 mS cm⁻¹ being exhibited by methyl butyl pyrrolidinium imide. Many of the salts are glass forming, exhibiting glass transition temperatures in the region of −90°C.

Crystal structure and ionic conductivity of a new bismuth tungstate,Bi3W2O10.5

The compound Bi3W2O10.5 was synthesized by the solid-state technique from Bi2O3 and WO3 in stoichiometric quantities. Single crystals were grown by the melt-cooling technique and the crystal structure was solved in the tetragonal 141in space group with a = 3.839 (1) A, c = 16-3S2 (5) A, V = 241.4 (1) angstrom(3), Z = 4 and was refined to an R index of 0.0672. The structure represents a modification of the Aurivillius phase and consists of [Bi2O2](2+) units separated by WO8 polyhedra. a.c. impedance studies indicate oxide ion conductivity of 2.91 10(-5) cm(-1) at 600 degrees C.

Synthesis, structure and ionic conductivity in scheelite type Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x=0 and 0.25, Ln = Pr, Sm)

Scheelite type solid electrolytes, Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x = 0 and 0.25, Ln = Pr, Sm) have been synthesized using a solid state method. Their structure and ionic conductivity (a) were obtained by single crystal X-ray diffraction and ac-impedance spectroscopy, respectively. X-ray diffraction studies reveal a space group of I4(1)/a for Li(0.5)Ce(0.5-x)Ln(x)MoO(4) (x = 0 and 0.25, Ln = Pr, Sm) scheelite compounds. The unsubstituted Li0.5Ce0.5MoO4 showed lithium ion conductivity similar to 10(-5)-10(-3) Omega(-1)cm(-1) in the temperature range of 300-700 degrees C (sigma = 2.5 x 10(-3) Omega(-1) cm(-1) at 700 degrees C). The substituted compounds show lower conductivity compared to the unsubstituted compound, with the magnitude of ionic conductivity being two (in the high temperature regime) to one order (in the low temperature regime) lower than the unsubstituted compound. Since these scheelite type structures show significant conductivity, the series of compounds could serve in high temperature lithium battery operations.

Structure and silver ion transport in AgI-Ag2MoO4 glasses: A molecular dynamics study

The structure and dynamics of silver ion conducting AgI-Ag2MoO4 glasses have been simulated by molecular dynamics simulation over a wide range of compositions. Formation of silver iodide like aggregates have been identified only in the AgI rich glasses. Increase in silver ion conductivity with an increase in AgI content in the glass is seen as in experiments. The dynamics of ion transport suggests that Ag+ ion transport occurs largely through paths connected by silver ion sites of mixed iodide-oxide coordination. The Van Hove correlation functions indicate that Ag+ ions prefer migration along the pathways formed with connected sites of similar coordination.

LiSr1.65 square 0.35B1.3B ' O-1.7(9) (B = Ti, Zr; B ' = Nb, Ta): New lithium ion conductors based on the perovskite structure

We describe the design and synthesis of new lithium ion conductors with the formula, LiSr(1.65)rectangle(0.35)B(1.3)B'O-1.7(9) (rectangle = vacancy; B = Ti, Zr; B' = Nb, Ta), on the basis of a systematic consideration of the composition-structure-property correlations in the well-known lithium-ion conductor, La-(2/3-x)Li(3x)rectangle((1/3)-2x)TiO3 (I), as well as the perovskite oxides in Li-A-B,B'-O (A = Ca, Sr, Ba; B = Ti, Zr; B' = Nb, Ta) systems. A high lithium-ion conductivity of ca. 0.12 S/cm at 360 degrees C is exhibited by LiSr(1.65)rectangle(0.35)Ti(1.3)Ta(1.7)O(9) (III) and LiSr(1.65)rectangle(0.35)Zr(1.3)Ta(1.7)O(9) (IV), of which the latter containing stable Zr(IV) and Ta(V) oxidation states is likely to be a candidate electrolyte material for all-solid-state lithium battery application. More importantly, we believe the approach described here could be extended to synthesize newer, possibly better, lithium ion conductors.

A new family of Ce6MoO15 as fast oxide ion conductor

A novel solid solution Ce6MoO15 was achieved. Their structure and oxide ionic conductivity were studied. Based on Ce6MoO15, rare earth element substitution on cerium site shows that all resulting oxides enhance the conductivity further, and have high oxide-ion conductivity, which may be a kind of promising material for SOFCs.

Ionic conductivity in poly(diethylene glycol-carbonate)/sodium triflate complexes

New polymer electrolytes were synthesized and characterized based on a new polymer host. The motivation was to produce a host polymer with a high dielectric constant which should reduce ion clustering with an attendant increased conductivity. The new polymer host, poly(diethylene glycol carbonate) and its sodium triflate complexes were characterized by thermal analysis and AC impedance measurements. The polycarbonate backbone appears less flexible than the polyether hosts as evidenced by the higher glass transition temperatures. The conductivity for the sodium triflate complexes was measured as ~ 10⁻⁵ S cm⁻¹ at 55 °C and the dielectric constant of the host polymer was found to be 3.6 at 3 GHz. The low conductivity is attributed to rigidity of the polycarbonate.

Structural studies of ambient temperature plastic crystal ion conductors

A number of novel organic ionic compounds based on the pyrrolidinium cation are described which have been found to be ion conductors in their solid states around room temperature. The properties of the compounds are consistent with their exhibiting plastic crystal phases. In order to understand some of the molecular origins of the plastic crystal behaviour and the ion conductivity that it promotes, a number of related compounds based on the imidazolium and ammonium cations are also described which have structural elements in common with the pyrrolidinium cation, but which do not show the plastic behaviour. It is found therefore that the nature of the cation is quite critical to the development of this behaviour. The alkyl methyl pyrrolidinium cation is found to produce plastic crystal phases when the alkyl chains are short, thereby preserving the ability of the cation to rotate with minimal steric hindrance. The ammonium and imidazolium cations of comparable size and structure are less able to produce these plastic phases, in many cases because the low temperature phase proceeds to melt rather than forming a stable rotator phase.

Bacterial cellulose/triethanolamine based ion-conducting membranes

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Development of the Oxide Ion Conductor Na0.5Bi0.5TiO3 (NBT) for Solid Oxide Cells

Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material with potential to replace lead zirconate titanate (PZT),1 however high leakage conductivity for the material has been widely reported.2 Through a combination of Impedance Spectroscopy (IS), O2- ion transference (EMF) number experiments and O18 tracer diffusion measurements, combined with Time-of-flight Secondary Ion Mass Spectrometry (TOFSIMS), it was identified that this leakage conductivity was due to oxygen ion conductivity. The volatilization of bismuth during synthesis, causing oxygen vacancies, is believed to be responsible for the leakage conductivity.3 The oxide-ion conductivity, when doped with magnesium, exceeds that of yttria-stabilized zirconia (YSZ) at ~500 °C,3 making it a potential electrolyte material for Intermediate Temperature Solid Oxide Cells (ITSOCs). Figure 1 shows the comparison of bulk oxide ion conductivity between 2 at.% Mg-doped NBT and other known oxide ion conductors.

As part of the UK wide £5.7m 4CU project, research has concentrated on trying to develop NBT for use in Intermediate Temperature Solid Oxide Cells (ITSOCS). With the aim of achieving mixed ionic and electronic conduction, transition metals were chemically doped on to the Ti-site. A range of experimental techniques was used to characterize the materials aimed at investigating both conductivity and material structure (Scanning Electron Microscopy (SEM), IS, X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS)). The potential for NBT as an ITSOC material, as well as the challenges of developing the material, will be discussed.

(1) Takenaka T. et al. Jpn. J. Appl. Phys 1999, 30, 2236.

(2) Hiruma Y. et al. J. Appl. Phys 2009, 105, 084112.

(3) Li. M. et al. Nature Materials 2013, 13, 31.

Effects of synthetic conditions on the structural, stability and ion conducting properties of Li0.30(La0.50Ln0.50)0.567TiO3 (Ln= La, Pr, Nd) solid electrolytes for rechargeable lithium batteries

The structure, thermal stability, morphology and ion conductivity of titanium perovskites with the general formula Li3xLn2/3−xTiO3 (Ln = rare earth element; 3x= 0.30) are studied in the context of their possible use as solid electrolyte materials for lithium ion batteries. Materials are prepared by a glycine-nitrate method using different sintering treatments, with a cation-disorder-induced structural transition from tetragonal to cubic symmetry, detected as quenching temperature increases. SEM images show that the average grain size increases with increasing sintering temperature and time. Slightly higher bulk conductivity values have been observed for quenched samples sintered at high temperature. Bulk conductivity decreases with the lanthanide ion size. A slight conductivity enhancement, always limited by grain boundaries, is observed for longer sintering times. TDX measurements of the electrolyte/cathode mixtures also show a good stability of the electrolytes in the temperature range of 30-1100ºC.