High-Conductive CsH2PO4 Membranes with PVDF-Based Polymers Additives.

The study is devoted to one of the important problems of hydrogen energy-the comparative analysis and creation of novel highly conductive and durable medium-temperature proton membranes based on cesium dihydrogen phosphate and fluoropolymers. The proton conductivity, structural characteristics and mechanical properties of (1 - x)CsH2PO4-x fluoropolymer electrolytes (x-mass fraction, x = 0-0.3) have been investigated and analyzed. UPTFE and PVDF-based polymers (F2M, F42, and SKF26) with high thermal stability and mechanical properties have been chosen as polymer additives. The used fluoropolymers are shown to be chemical inert matrices for CsH2PO4. According to the XRD data, a monoclinic CsH2PO4 (P21/m) phase was retained in all of the polymer electrolytes studied. Highly conductive and mechanically strong composite membranes with thicknesses of ~50-100 µm were obtained for the soluble fluoropolymers (F2M, F42, and SKF26). The size and shape of CsH2PO4 particles and their distribution have been shown to significantly affect proton conductivity and the mechanical properties of the membranes. The thin-film polymer systems with uniform distributions of salt particles (up to ~300 nm) were produced via the use of different methods. The best results were achieved via the pretreatment of the suspension in a bead mill. The ability of the membranes to resist plastic deformation increases with the growth of the polymer content in comparison with the pure CsH2PO4, and the values of the mechanical strength characteristics are comparable to the best low-temperature polymer membranes. The proton-conducting membranes (1 - x)CsH2PO4-x fluoropolymer with the optimal combination of the conductivity and mechanical and hydrophobic properties are promising for use in solid acid fuel cells and other medium-temperature electrochemical devices.

Copolymer of VDF/TFE as a Promising Polymer Additive for CsH2PO4-Based Composite Electrolytes.

The composite polymer electrolytes (1-x)CsH2PO4-xF-2M (x = 0-0.3) have been first synthesized and their electrotransport, structural, and mechanical properties were investigated in detail by impedance, FTIR spectroscopy, electron microscopy, and X-ray diffraction methods. The structure of CsH2PO4 (P21/m) with salt dispersion is retained in the polymer electrolytes. The FTIR and PXRD data are consistent, showing no chemical interaction between the components in the polymer systems, but the salt dispersion is due to a weak interface interaction. The close to uniform distribution of the particles and their agglomerates is observed. The obtained polymer composites are suitable for making thin highly conductive films (60-100 µm) with high mechanical strength. The proton conductivity of the polymer membranes up to x = 0.05-0.1 is close to the pure salt. The further polymers addition up to x = 0.25 results in a significant decrease in the superproton conductivity due to the percolation effect. Despite a decrease, the conductivity values at 180-250 °C remain high enough to enable the use of (1-x)CsH2PO4-xF-2M as a proton membrane in the intermediate temperature range.

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.

Crystal structure and proton conductivity of a new Cs3(H2PO4)(HPO4)·2H2O phase in the caesium di- and monohydrogen orthophosphate system.

The MxHy(AO4)z acid salts (M = Cs, Rb, K, Na, Li, NH4; A = S, Se, As, P) exhibit ferroelectric properties. The solid acids have low conductivity values and are of interest with regard to their thermal properties and proton conductivity. The crystal structure of caesium dihydrogen orthophosphate monohydrogen orthophosphate dihydrate, Cs3(H1.5PO4)2·2H2O, has been solved. The compound crystallizes in the space group Pbca and forms a structure with strong hydrogen bonds connecting phosphate tetrahedra that agrees well with the IR spectra. The dehydration of Cs3(H1.5PO4)2·2H2O with the loss of two water molecules occurs at 348-433 K. Anhydrous Cs3(H1.5PO4)2 is stable up to 548 K and is then converted completely into caesium pyrophosphate (Cs4P2O7) and CsPO3. Anhydrous Cs3(H1.5PO4)2 crystallizes in the monoclinic C2 space group, with the unit-cell parameters a = 11.1693 (4), b = 6.4682 (2), c = 7.7442 (3) Šand ß = 71.822 (2)°. The conductivities of both compounds have been measured. In contrast to crystal hydrate Cs3(H1.5PO4)2·2H2O, the dehydrated form has rather low conductivity values of ∼6 × 10-6-10-8 S cm-1 at 373-493 K, with an activation energy of 0.91 eV.