Commercial polyether-etherketone was sulfonated and reacted with SiCl4 to obtain a hybrid polymer. Polymers having different inorganic content were characterized by 29Si NMR, ATR/FTIR spectroscopies and mass spectrometry (FAB-MS) demonstrating the formation of covalent bonds between the organic and inorganic components and the absence of dispersed inorganic silicon. The physicochemical properties of the hybrids were suitable for the preparation of membranes which showed sufficiently high conductivity values to make them promising candidates for application in PEMFCs.

All solid-state ceramic lithium battery was studied using a composite anode, the thio-LISICON (Li3.25Ge0.25P0.75S4) solid electrolyte, and the Chevrel phase cathode. The nano-composite of cathode configuration reduced the interfacial resistance and provided fast-charge transfer at the interface. The self-assembled solid-electrolyte interfacial (SEI) phase was formed at the Li-Al/SE interface, while no formation was observed at the Li-In/SE interface. The SEI phase reduced the interfacial resistance and provided high charge-discharge characteristics. The all solid-state cell showed high current density of 1.3C rate and is a promising candidate for future lithium battery system.

Bond valence mismatch landscapes may serve as simple models of the effective energy landscapes for mobile ions in solid electrolytes. Thereby they provide a tool to identify the ion transport mechanism and allow to predict the activation energy of the ionic conduction. Accounting for the mass dependence of the conversion from the BV mismatch into an activation energy scale yields a correlation that holds for different types of mobile cations. While in most cases the analysis of bond valence mismatch landscapes is consistent with the ion transport mechanism derived from experimental or other computational evidence, the presumed prototype of trivalent cation conductors Sc2(WO4)3 is discussed as an example, where the BV analysis of transport pathways suggests that the interpretation of previous experimental investigations has to be reconsidered. Both bond valence calculations and molecular dynamics simulations suggests that the most probable mobile species in stoichiometric Sc2(WO4)3 is neither Sc3+ nor individual O2- but the complex divalent anion WO42-.

The suspensions of yttria stabilized zirconia (YSZ) were prepared in pure acetylacetone and ethanol and their mixtures. In all of the suspensions, YSZ thin films were obtained using electrophoretic deposition technique on the substrates of stainless steel and porous strontium-doped lanthanum manganite (LSM) which is a typical cathode materials used in solid oxide fuel cells (SOFCs). The deposition behavior in the different suspensions was studied. The deposited films were dried at room temperature and then sintered at high temperature. Observation with scanning electron microscopy (SEM) showed the sintered YSZ were of high density.

Thin films of BaCe0.8Y0.2O3-δ (BCY) were prepared by colloidal spray deposition. Dense, crack-free BCY films having a grain size of 2–7 μm were successfully deposited on NiO/BCY substrates. Electrochemical hydrogen pumping with the BCY films showed that the maximum current density increased with temperature. The maximum current density was sensitive to the moisture in the cathode gas; the value obtained with a dry cathode gas was only half that with a wet cathode gas. A very high hydrogen-pumping current density of 3.4 A/cm2 was measured at 700°C with an applied voltage of 1.5 V.

Amongst solid solutions of the Li-Ni-Mn-Co-O series, LiNi1/3Mn1/3Co1/3O2 has received much attention owing to its high capacity and thermal stability. A major issue in these ordered rock salt structures is the irreversibility on the first cycle, and degree of Li+/Ni2+ cation disorder which inhibits the rate capability. To examine these factors, different synthesis methods were employed which led to LiNi1/3Mn1/3Co1/3O2 that exhibited varying degrees of cation disorder. Neutron diffraction studies were carried out on samples (LixNi1/3Mn1/3Co1/3O2, x = 1.00 → 0.04) prepared by chemical oxidation. The studies reveal that the extent of Ni2+/Li+ disorder between the 3b and 3a sites was preserved on Li extraction and re-insertion. Complete extraction of lithium to form the O1 phase was achieved in some materials. However, reformation of the O3 phase on chemical relithiation does not occur in these cases, whereas materials that only partly convert to the Ol phase exhibit complete conversion back to the O3 phase on relithiation. The differences are attributed to lithium site occupancy/stoichiometry and crystallite size effects.

Ordered-mesoporous-Al2O3 was synthesized by the sol-gel route using neutral copolymer surfactants as templates. The pore size was controlled over the range of 3∼22 nm by using different surfactant copolymers under different synthetic conditions. Protonic conductivity of hydrated mesoporous alumina was examined for CIP treated mesoporous alumina pellet. The highest protonic conductivity was obtained as 0.004 S· cm−1 at 25 °C under 80% RH for the pellet with 15 nm averaged pores. The conductivity increased monotonically with increasing pore size under constant humidity. Quantitative determination of the concentration and the mobility of protons in hydrated mesoporous alumina was performed by 1H NMR, quasi-elastic neutron scattering (QENS) and TG/DTA measurements. Both the mobility and the concentration increased with increasing pore size. On the other hand, composites composed of synthesized mesoporous-Al2O3 and lithium iodide (LiI) was prepared. Dc electrical conductivity of 50LiI.50(mesoporous-Al2O3) was 2.6×10−4 S cm−1 at room temperature, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which the conductivity increased with decreasing the pore size except for pore size=3 nm. The 7Li diffusion constant of the composite was investigated by QENS as well as pulsed field gradient nuclear magnetic resonance (PFG-NMR). The dc conductivities showed reasonable agreement with an Einstein equation using measured diffusion constants.

An original process for the preparation of YSZ dense films with a thickness lower than 10 μm over NiO-YSZ substrates is presented. This process involves the preparation of a green membrane of NiO-YSZ and subsequent electrophoretic deposition (EPD) of commercial YSZ powder on this polymer-rich membrane. A single thermal treatment allowed removal of the organic compounds, sintering of the layers and full densification of the electrolyte.

Research on hydrogen separation membranes is motivated by the increasing demand for an environmentally benign, inexpensive technology for separating hydrogen from gas mixtures. Although most studies of hydrogen separation membranes have focused on proton-conducting oxides by themselves, the addition of metal to these oxides increases their hydrogen permeability and improves their mechanical stability. This study began by determining the electrical and hydrogen permeation properties of SrCe0.8Yb0.2O3−δ (SCYb). The results showed that the hydrogen permeation rate is limited by electron flow at the investigated temperatures (600 – 900°C). To further enhance hydrogen permeability, a cermet (i.e., ceramic-metal composite) membrane was made by adding Ni to the SCYb. The cermet showed no phase change after sintering in a reducing atmosphere. At 900°C, with 20% H2 /balance He as a feed gas (pH2O = 0.03 atm), the hydrogen permeation rate was 0.113 cm3/min-cm2 for Ni/SCYb (0.43-mm thick) and 0.008 cm3/min-cm2 for SCYb (0.7-mm thick). The dependences of hydrogen permeability on temperature, thickness, and hydrogen partial pressure gradients are also determined. The results demonstrate that adding Ni to SCYb considerably increases its hydrogen permeability by increasing its electron conductivity.

As the youngest battery chemistry, Li ion technology was made possible by the formation of stable electrode/electrolyte interfaces. The correlation between the electrochemistry and the surface profile of the graphitic anode was studied in this work with a new salt lithium bis (oxalate) borate (LiBOB).

In an attempt to depict a dynamic picture of the formation of graphite/electrolyte interface during the initial forming cycle, we employed X-ray photoelectron spectroscopy in combination with the “pre-formation” technique to establish the dependence of the surface chemistry on the forming potential of the anode. A progressive transition in the 1s electron binding energies of the major elements was observed as the lithiation proceeds; however, the surface chemical species as well as their abundances seemed to stabilize around 0.55 V and remained constant during the subsequent delithiation process, indicating that a stable solid electrolyte interface (SEI) exists thereafter. Integrating the information revealed by different analyses, we believe that the reductive decomposition of BOB−-anion starts at ca. 1.00 V, while the effective protection of graphene surface by SEI is available after the anode is lithiated below the potential of 0.55 V.

La0.8Sr0.2Ga0.8Mg0.2-xCoxO3-δ (LSGMC) powders containing different amounts of Co (x = 0.05 and 0.085) were prepared by a citrate sol-gel method. Crystalline powders were obtained by firing at 1000°C (10 h) and dense high-purity pellets were prepared by pressing (300 MPa) and sintering in air at 1475°C (5, 10 and 20 h). The sintered pellets of LSGMC were characterized by X-Ray Diffraction (XRD) Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The conductivity of sintered LSGMC pellets containing different amounts of Co ions in the B sites of the perovskite lattice was assessed by electrochemical impedance spectroscopy (EIS) in the 250–750 °C temperature range. Conductivity values and apparent activation energies were in good agreement with previously published data referring to materials with same composition, but prepared by solid-state reaction.

Autonomous MEMS require similarly miniaturized power sources. We present the first three-dimensional (3D) working thin-film microbattery (MB) technology that is compatible with MEMS requirements. Our 3D MBs are formed in perforated substrates (silicon chip or glass microchannel plate), in which a sandwich-like thin-film battery structure is deposited conformally and sequentially on all available surfaces, using wet chemistry. The area of high aspect ratio holes in the substrate enhances the capacity and energy density per given substrate footprint by more than an order of magnitude. Full 3D cells were manufactured on both glass and silicon substrates. A 3D cell on a micro-channel plate substrate exhibited a capacity of ca. 2mAh/cm2, in good agreement with the ca. 23 times area gain provided vs an identical footprint 2D cell.

The reversible Li-driven copper extrusion/insertion mechanism into Cu2.33V4O11 electrode has been studied and a new ion-exchanged assisted electrochemical process was unravelled. This process, entails during the charging of “Lix V4O11 + Cu0” composite electrodes vs. Li, the oxidation of Cu metal into copper ions that concomitantly exchanged for lithium ions to produce back Cu2.33V4O11. The electrochemical performances of such cells, namely in terms of capacity retention and power rates, are explained on the basis of the electrochemically generated Cu ions that can either being ion-exchanged with Li within the Li-V-O host or released in the solution. When the former does occur we show, owing to excellent kinetic of both, the ion-exchanged reaction between Cu2+ and Li+ together with a fast charge transfer between Cu0 and Cu2+, that high rate performances electrodes can be achieved whereas when the latter prevails the cells rapidly fail. It appears then that Cu+ ions should be removed. Thus, a new copper vanadate Cu1.1V4O11 phase has been isolated by both chemical and electrochemical removal of Cu from the mother Cu2.33V4O11 phase, and its electrochemical performance in Li cells studied. The removal of copper was shown to occur in a topotactic manner resulting in a stacking of [V4O11]n layers linked by differently coordinated copper ions. This new phase reversibly reacts with 5 Li, leading to a capacity of about 260 mAh/g, through a process involving a reversible displacement reaction entailing to the growth/disappearance of Cu dendrites.

Dense ceramics with composition Ba(Ce0.7Zr0.2Yb0.1)O3-β (BCZY) were synthesized by solid state reactions, and their structures were characterized by Rietveld refinements of time-of-flight (TOF) neutron diffraction data collected for the samples at high-temperature and controlled atmospheres. The structure phase transition from orthorhombic Imma to cubic Pm3m was observed at the temperature between 500 and 700°C and in flowing 100ppm H2/Ar gases. At 900°C, the sample was subsequently exposed to different oxygen partial pressures (pO2, ranging from ∼10−17 to ∼10−23 atm) and water vapor pressures (pH2O) up to ∼0.18 atm. The expansion of lattice parameters of BCZY, instead of following the normally expected relationship with pO2, was actually correlated with the increase of pH2O, implying proton incorporation into the structures. The presence of H-containing species in the structure was confirmed by comparing both inelastic neutron scattering spectra and neutron diffraction data collected for dry and “wet” samples at 10K. The observed vibrational peaks at 104 and 150 meV and absence of a peak around 420 meV indicate the hydrogen occupation in the structure but the absence of any hydroxyl groups (hydrogen covalently bonded to oxygen). Electrical conductivities of BCZY were investigated at different temperatures in both dry and wet conditions.

Hydrous RuO2 is a mixed metallic-protonic conductor that is used as a charge storage material in electrochemical capacitors and as an electrocatalyst. Previous structural analysis by Dmowski, et. al. has shown that RuO2 is a composite of ordered RuO2 nanoparticles that are surrounded by hydrous grain boundaries. In this paper, magnetic susceptibility (MS) is used to show that the hydrous RuO2 has both localized and delocalized electrons. The localized electrons are attributed to Ru3+ defects that decrease in concentration with decreasing water content. The delocalized electrons are represented by a temperature independent paramagnetic (TIP) component of the MS. The magnetic data is consistent with a structure having metallic nanoparticles whose electrons become more itinerant with decreasing structural water. We conclude that hydrous RuO2 stores charge analogously to double-layer capacitors in which charge is stored at the interface of the hydrous grain boundaries and the metallic nanoparticles, and that there is effectively no difference in the charge storage mechanisms of hydrous RuO2 and carbon.

Two conceptions of oxygen selective membrane's development, ceramic and thin film ones were considered using perovskite Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) with mixed oxygen ionic and electronic conductivity. The films of BSCF (2–3mkm thick) were deposited by a MOCVD technique on the porous substrates (YSZ, Al2O3). Gas tightness, selective oxygen flux at 750–950°C and stability of the asymmetric film membranes in working conditions were investigated in comparison with ceramic ones. Sufficiently gas tight films can be directly obtained only on the substrates with submicron pores and at Tdep < 600°C. New alternative approach of large-pore substrates modification for obtaining gas-tight oxygen selectively permeable membranes was developed. To avoid the chemical interaction between BSCF and YSZ or Al2O3 the intermediate layer of BaO was pre-deposited. Resulting permeation through asymmetric membranes was thought to be dependent on oxygen exchange surface reaction and gas permeability of the porous supports.

In order to stabilize the fast oxide ion conducting properties of the high temperature form of Ba2In2O5 at lower temperature, oxygen rich doped Ba2In2O5+δ brownmillerite were prepared by partial substitution of Ba and In with higher valence cation. Vanadium, niobium, tantalum, molybdenum and tungsten were introduced on indium site and bismuth on barium site. Solid solutions were evidenced in all the cases. They were characterized by high temperature X-ray diffraction and impedance spectroscopy. A neutron diffraction study was carried out and allowed to extract preferential oxygen pathways in these materials.

Results of simple computer simulations and model calculations for ion conducting rotor phases are compared to quasi-elastic neutron scattering data from solid solutions of sodium orthophosphate and sodium sulphate, xNa2SO4 · (1 — x)Na3PO4. These materials are not only sodium fast-ion conductors in their high-temperature cubic phases but also show considerable dynamic reorientation disorder of their tetrahedral anions.

At an elastic energy resolution of about 100 μeV, neutron spectrometry monitored oxygen scattering due to anion reorientation which occurs on the picosecond time scale. This thermally activated process exhibits activation energies between 0.184 eV (x = 0. 0) and 0.052 eV (x = 0.5). Analysis of the quasielastic intensities as a function of scattering vector Q gives clear evidence of the involvement of cations in the anion reorientation.

Increasing the elastic resolution to about 1 μeV FWHM (thereby shifting the dynamic window to the nanosecond scale) allowed to examine sodium diffusion in x Na2SO4 · (1 — x)Na3PO4. This process consists predominantly of thermally-activated jumps between tetrahedrally coordinated sites, the activation energies ranging from 0.64 eV for x = 0.0 to 0.30 eV for x = 0.5.

We synthesized perovskite-type Li ion conductor, (La2/3–1/3p Lip)(Mg1/2W1/2)O3 (p =0.05, 0.11 and 0.14), and investigated the variation of the Li ion conductivity with p. Furthermore, the variation of the activation energy with the valence of B-site ion was elucidated from the site potential at A-site and a bottleneck position. As results, it is suggested that the Coulomb repulsion between B-site and Li ions at the bottleneck dominates the activation energy for (La2/3–1/3p Lip)(Mg1/2W1/2)O3.

We have prepared Ni-V2O5·nH2O core-shell nanocable arrays for Li+ intercalation applications. Ni-V2O5·nH2O nanocables were prepared via formation of Ni nanorod arrays through the template based electrochemical deposition, followed by coating of V2O5·nH2O on Ni nanorods through electrophoretic deposition. Transmission electron microscopy (TEM) micrograph clearly shows the Ni core was covered completely by a V2O5·nH2O shell. Electrochemical analysis demonstrates that in a current density of 1.6 A/g, the Li+ intercalation capacity of Ni-V2O5·nH2O nanocable array is approximately 10 times higher than that of single-crystal V2O5 nanorod array and 20 times higher than that of sol-gel-derived V2O5 film. Both energy density and power density of such nanocable-array electrodes are higher than the V2O5 film electrode by at least one order of magnitude. Such significant improvement in electrochemical performance is due to the large surface area and short diffusion path offered by the nanostructured V2O5·nH2O.