Hybrid Nanocomposite Solid Electrolytes (n-C4H9)4NBF4-MgO.

Hybrid nanocomposite materials Bu4NBF4-MgO were obtained using a nanocrystalline MgO with a specific surface area of 324 m2/g and the grains size of 5.1 nm. As a result of the strong adhesion, the salt transforms into an interface-stabilized amorphous state within the thin layer near the interface. The analysis of the DSC data allowed one to estimate the concentration and the thickness of this amorphous layer as 4.8 nm. The amorphous interface phase has an enhanced ionic conductivity. As a result, conductivity of the nanocomposite increases with the concentration of the amorphous phase and reaches 1.1 × 10-3 S/cm at 150 °C at a concentration of the MgO additive x = 0.90 corresponding to the maximum content of the amorphous phase. The conductivity of the nanocomposite is by three orders of magnitude higher than the conductivity of pure Bu4NBF4. The nanocomposites are electrochemically stable up to 2.5 V. At high concentrations of MgO when the total volume of the salt is small the composites become nano- and mesoporous.

Stabilization of the (C2H5)4NHSO4 High-Temperature Phase in New Silica-Based Nanocomposite Systems.

In this study, the electrotransport, thermal and structural properties of composite solid electrolytes based on (C2H5)4NHSO4 plastic phase and silica (1 - x)Et4NHSO4-xSiO2, where x = 0.3-0.9) were investigated for the first time. The composites were prepared by mechanical mixing of silica (300 m2/g, Rpore = 70Å) and salt with subsequent heating at temperatures near the Et4NHSO4 melting point. Heterogeneous doping is shown to change markedly the thermodynamic and structural parameters of the salt. It is important that, with an increase in the proportion of silica in the composites, the high-temperature disordered I41/acd phase is stabilized at room temperature, as this determines the properties of the system. Et4NHSO4 amorphization was also observed in the nanocomposites, with an increase in the matrix contents. The enthalpies of the endoeffects of salt melting and phase transitions (160 °C) changed more significantly than the Et4NHSO4 contents in the composites and completely disappeared at x = 0.9. The dependence of proton conductivity on the mole fraction reached a maximum at x = 0.8, which was three or four orders of magnitude higher than the value for pure Et4NHSO4, depending on the composition and the temperature. The maximum conductivity values were close to those for complete pore filling. The conductivity of the 0.2Et4NHSO4-0.8SiO2 composite reached 7 ∗ 10-3 S/cm at 220 °C and 10-4 S/cm at 110 °C.

Resolving old problems with layered polytungstates related to hexagonal tungsten bronze: phase formation, structures, crystal chemistry and some properties.

A 60-year-old problem with the atomic arrangements and exact compositions of alkali polytungstates related to hexagonal tungsten bronze (HTB) was solved. The systems A2WO4-WO3 (A = K, Rb) were restudied and the average monoclinic layered structures of stoichiometric polytungstates A4W11O35 (A = K, Rb, Cs, Tl) and A2W7O22 (A = K, Rb, Cs) were first successfully determined. The structures resemble those of "MoW11O36" and "MoW14O45" (J. Graham and A. D. Wadsley, Acta Crystallogr., 1961, 14, 379-383) and are derived from HTB by breaking into slabs parallel to (100) due to the ordered omission of some [WO]∞ chains along the hexagonal tunnels. The slabs in A4W11O35 (A = Cs, Tl) and A2W7O22 (A = Rb, Cs) are mutually shifted by the a/2 HTB unit cell axis. These data mainly confirmed our preliminary structural models of HTB-like alkali polytungstates (S. F. Solodovnikov, N. V. Ivannikova, Z. A. Solodovnikova and E. S. Zolotova, Inorg. Mater., 1998, 34, 845-853) and revealed a new similar thallium polytungstate. The structures of the HTB-like polytungstates and related compounds form a homologous series of layered complex oxides or fluorides An+2-xM3n+2X9n+8 where n = 2, 3 and 4 are equal to the numbers of HTB hexagonal tunnels across the polytungstate slab width for Tl2W4O13, A4W11O35 and A2W7O22 (A = K, Rb, Cs or Tl), respectively. The structures of the HTB-like polytungstates seem to intergrow with HTB-type AxWO3 to form, in particular, higher homologues of the series. Our group-supergroup analysis, measurements of nonlinear optical activity and electrical conductivity, and calculations of the bond-valence site energy barriers indicate possible ferroelectric/ferroelastic properties and moderate 2D oxide-ion mobility within the HTB-type slabs of the studied polytungstates.

Transport and Electrochemical Properties of Li4Ti5O12-Li2TiO3 and Li4Ti5O12-TiO2 Composites.

The study demonstrates that the introduction of the electrochemically inactive dielectric additive Li2TiO3 to LTO results in a strong decrease in the grain boundary resistance of LTO-Li2TiO3 (LTC) composites at a low concentration of Li2TiO3. With the increase in the concentration of Li2TiO3 in LTC composites, the grain boundary resistance goes through a minimum and increases again due to the growth of the insulation layer of small Li2TiO3 particles around LTO grains. For LTO-TiO2 (LTT) composites, a similar effect was observed, albeit not as strong. It was found that LTC composites at low concentration of Li2TiO3 have unusually high charge-discharge capacity exceeding the theoretical value for pure LTO. This effect is likely to be caused by the occurrence of the electrochemical activity of Li2TiO3 in the vicinity of the interfaces between LTO and Li2TiO3. The increase in the capacity may be qualitatively described in terms of the model of two-phase composite in which there is the interface layer with a high capacity. Contrasting with LTC composites, in LTT composites, no capacity enhancement was observed, which was likely due to a noticeable difference in crystal structures of LTO and TiO2 preventing the formation of coherent interfaces.

Effect of Pore Filling on Properties of Nanocomposites LiClO4-MIL-101(Cr) with High Ionic Conductivity.

Experimental data on nitrogen adsorption, pellets density and ionic conductivity of nanocomposite solid electrolytes (1−x)LiClO4−xMIL-101(Cr) were interpreted in frames of the model of the composite in which the lithium salt fills the pores of a metal-organic framework MIL-101(Cr). According to the model, the concentration of lithium salt located in the pores reaches a maximum at the concentration x = xmax which is defined by a ratio of the molar volume of LiClO4 and the total volume of accessible pores in the MIL-101(Cr) framework. The model allows one to describe the dependences of pore volume and pellet density on the concentration of MIL-101(Cr). Conductivity of the composites were successfully described by two separate mixing equations for concentration ranges x < xmax and x > xmax. In the first concentration region x < xmax, the composite may be regarded as a mixture of LiClO4 and MIL-101(Cr) with completely filled pores accessible for LiClO4. At x > xmax, the total amount of lithium perchlorate is located in the pores of MIL-101(Cr) and occupies only part of the volume of the accessible pores. It was found that xmax value determined from the concentration dependence of conductivity (xmax = 0.06) is noticeably lower than the corresponding value estimated from adsorption data (xmax = 0.085) indicating a practically complete filling the pores of MIL-101(Cr) in the composite pellets heated before conductivity measurements.

Structural and Transport Properties of E-Beam Sintered Lanthanide Tungstates and Tungstates-Molybdates.

Lanthanide tungstates and molybdates are promising materials for hydrogen separation membranes due to their high protonic conductivity. A promising approach to fabricating ceramics based on these materials is radiation thermal sintering. The current work aims at studying the effect of radiation thermal sintering on the structural morphological and transport properties of (Nd,Ln)5.5(W,Mo)O11.25-δ as promising materials for hydrogen separation membranes. The defect fluorite structure was shown to be preserved during radiation thermal sintering at 1100 °C. The presence of protons in hydrated samples was confirmed by TGA. According to four-electrode studies and the isotope exchange of oxygen with C18O2, the samples demonstrate a high proton conductivity and oxygen mobility. Residual porosity (up to 29%) observed for these samples can be dealt with during membrane preparation by adding sintering aids and/or metal alloys nanoparticles. Hence, sintering by e-beams can be applied to the manufacturing of hydrogen separation membranes based on these materials.

Ionic Transport in CsNO2-Based Nanocomposites with Inclusions of Surface Functionalized Nanodiamonds.

Composite solid electrolytes (1-x) CsNO2-xND, where ND are nanodiamonds, including those after liquid-phase and gas-phase oxidation and reduction functionalization, were prepared, and their properties investigated by XRD, analysis of BET nitrogen adsorption isotherms, IR spectroscopy and impedance spectroscopy. The electrical conductivity of composites (1-x) CsNO2-xND obeys the Arrhenius dependence and has a maximum at x = 0.95 regardless of the ND pretreatment. It was found that the conductivity depends on the mode of functionalization of the ND surface, as well as on the processing time. The electrical conductivity of composites with ND, processed by the gas-phase method, is 1.5-2.6 times higher than that of composites with initial ND, in which the conductivity is 2 orders of magnitude higher than that of pure cesium nitrate. Thus, the possibility of using ND as an effective heterogeneous additive for the preparation of composite solid electrolytes, including cesium nitrite, has been demonstrated for the first time.

Triple molybdates K3-xNa1+xM4(MoO4)6 (M = Ni, Mg, Co) and K3+xLi1-xMg4(MoO4)6 isotypic with II-Na3Fe2(AsO4)3 and yurmarinite: synthesis, potassium disorder, crystal chemistry and ionic conductivity.

The triple molybdates K3-xNa1+xM4(MoO4)6 (M = Ni, Mg, Co) and K3+xLi1-xMg4(MoO4)6 were found upon studying the corresponding ternary molybdate systems, and their structures, thermal stability and electrical conductiviplusmnty were investigated. The compounds crystallize in the space group R3c and are isostructural with the sodium-ion conductor II-Na3Fe2(AsO4)3 and yurmarinite, Na7(Fe3+, Mg, Cu)4(AsO4)6; their basic structural units are flat polyhedral clusters of the central M1O6 octahedron sharing edges with three surrounding M2O6 octahedra, which combine with single NaO6 octahedra and bridging MoO4 tetrahedra to form open three-dimensional (3D) frameworks where the cavities are partially occupied by disordered potassium (sodium) ions. The split alkali-ion positions in K3-xNa1+xM4(MoO4)6 (M = Ni, Mg, Co) give their structural formulae as [(K,Na)0.5□0.5)]6(Na)[M1][M2]3(MoO4)6, whereas the lithium-containing compound (K0.5□0.5)6(Mg0.89K0.11)(Li0.89Mg0.11)Mg3(MoO4)6 shows an unexpected (Mg, K) isomorphism, which is similar to (Mn, K) and (Co, K) substitutions in isostructural K3+xLi1-xM4(MoO4)6 (M = Mn, Co). The crystal chemistry of the title compounds and related arsenates, phosphates and molybdates was considered, and the connections of the cationic distributions with potential 3D ionic conductivity were shown by means of calculating the bond valence sum (BVS) maps for the Na+, Li+ and K+ ions. Electrical conductivity measurements gave relatively low values for the triple molybdates [σ = 4.8 × 10-6 S cm-1 at 390°C for K3NaCo4(MoO4)6 and 5 × 10-7 S cm-1 at 400°C for K3LiMg4(MoO4)6] compared with II-Na3Fe2(AsO4)3 (σ = 8.3 × 10-4 S cm-1 at 300°C). This may be explained by a low concentration of sodium or lithium ions and the blocking of their transport by large potassium ions.