Interface Diffusion and Compatibility of (Ba,La)FeO3-δ Perovskite Electrodes in Contact with Barium Zirconate and Ceria.

Ba1-xLaxFeO3-δ perovskites (BLF) capable of conducting electrons, protons, and oxygen ions are promising oxygen electrodes for efficient solid oxide cells (fuel cells or electrolyzers), an integral part of prospected large-scale power-to-gas energy storage systems. We investigated the compatibility of BLF with lanthanum content between 5 and 50%, in contact with oxide-ion-conducting Ce0.8Gd0.2O2-δ and proton-conducting BaZr0.825Y0.175O3-δ electrolytes, annealing the electrode-electrolyte bilayers at high temperature to simulate thermal stresses of fabrication and prolonged operation. By employing both bulk X-ray diffraction and synchrotron X-ray microspectroscopy, we present a space-resolved picture of the interaction between electrode and electrolyte as what concerns cation interdiffusion, exsolution, and phase stability. We found that the phase stability of BLF in contact with other phases is correlated with the Goldschmidt tolerance factor, in turn determined by the La/Ba ratio, and appropriate doping strategies with oversized cations (Zn2+, Y3+) could improve structural stability. While extensive reactivity and/or interdiffusion was often observed, we put forward that most products of interfacial reactions, including proton-conducting Ba(Ce,Gd)O3-δ and mixed-conducting (Ba,La)(Fe,Zr,Y)O3-δ, may not be very detrimental for practical cell operation.

Ion transport mechanism in anhydrous lithium thiocyanate LiSCN Part I: ionic conductivity and defect chemistry.

This work reports on the ion transport properties and defect chemistry in anhydrous lithium thiocyanate Li(SCN), which is a pseudo-halide Li+ cation conductor. An extensive doping study was conducted, employing magnesium, zinc and cobalt thiocyanate as donor dopants to systematically vary the conductivity and derive a defect model. The investigations are based on impedance measurements and supported by other analytical techniques such as X-ray powder diffraction (XRPD), infrared (IR) spectroscopy, and density functional theory (DFT) calculations. The material was identified as Schottky disordered with lithium vacancies being the majority mobile charge carriers. In the case of Mg2+ as dopant, defect association with lithium vacancies was observed at low temperatures. Despite a comparably low Schottky defect formation enthalpy of (0.6 ± 0.3) eV, the unexpectedly high lithium vacancy migration enthalpy of (0.89 ± 0.08) eV distinguishes Li(SCN) from the chemically related lithium halides. A detailed defect model of Li(SCN) is presented and respective thermodynamic and kinetic data are given. The thiocyanate anion (SCN)- has a significant impact on ion mobility due to its anisotropic structure and bifunctionality in forming both Li-N and Li-S bonds. More details about the impact on ion dynamics at local and global scale, and on the defect chemical analysis of the premelting regime at high temperatures are given in separate publications (Part II and Part III).

Ion transport mechanism in anhydrous lithium thiocyanate LiSCN part III: charge carrier interactions in the premelting regime.

In lithium thiocyanate Li(SCN), the temperature regime below the melting point (274 °C) is characterized by excess conductivities over the usual Arrhenius behavior (premelting regime). Here, the Schottky defect pair concentration is high, and the point defect chemistry can no longer be considered as dilute. Coulomb interactions of Schottky pairs are expected to occur lowering the formation energy of new carriers and hence leading avalanche-like to a transition into a fully defective superionic state. The respective non-linear behavior is investigated using the cube-root law approach characterized by a defect interaction parameter J, which is a measure of the effective defect-lattice energy. In the case of Li(SCN), the rather pronounced volume expansion is to be included in the model. A literature comparison with other materials emphasizes to what degree defect formation as well as defect interactions depend not only on the dominant mobile defect, but also on the respective sublattice. Overall, a quantitative description of the defect chemistry of Li(SCN) in the premelting regime is derived.

Ion transport mechanism in anhydrous lithium thiocyanate LiSCN part II: frequency dependence and slow jump relaxation.

Specific aspects of the Li+ cation conductivity of anhydrous Li(SCN) are investigated, in particular the high migration enthalpy of lithium vacancies. Close inspection of impedance spectra and conductivity data reveals two bulk relaxation processes, with comparatively fast ion transport at high frequencies and slow ion migration at low frequencies. The impedance results are supported by solid state nuclear magnetic resonance (ssNMR), and pair distribution function (PDF) analysis. This behavior reflects a frequency dependent conductivity, which is related to the extremely slow thiocyanate (SCN)- anion lattice relaxation that occurs when a Li+ cation jumps to the next available site. Two possible migration models are proposed: the first model considers an asymmetric energy landscape for Li+ cation hopping, while the second model is connected to the jump relaxation model and allows for 180° rotational disorder of the (SCN)- anion. A complete kinetic analysis for the hopping of Li+ cations is presented, which reveals new fundamental insights into the ion transport mechanism of materials with complex anions.

Synthesis, characterization and thermal behaviour of solid phases in the quasi-ternary system Mg(SCN)2-H2O-THF.

Mg(SCN)2·4H2O can be converted into previously unknown compounds Mg(SCN)2·(4 - x) H2O·xTHF with x = 0, 2 and 4 by multiple recrystallization in tetrahydrofuran (THF). The phases were characterized by infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), and their crystal structures were solved from X-ray powder diffraction (XRPD) data. In the crystal structures isolated Mg(NCS)2(H2O)4-x(THF)x units form layered motifs. The thermal behavior of Mg(SCN)2·4H2O and Mg(SCN)2·4THF was investigated by temperature dependent in situ XRPD, where Mg(SCN)2·4THF was found to acquire a room temperature (α-form) and high temperature modification (ß-form). The phase transformation is associated with an order-disorder transition of the THF molecules and with a reversion of the stacking order of the layered motifs. Further heating eventually leads to the formation of Mg(SCN)2·2THF. There thiocyanate related sulfur atoms fill the voids in the coordination sphere of magnesium, which leads to the formation of one dimensional electroneutral ∞[Mg(NCS)2/2(SCN)2/2(THF)2] chains. All investigated Mg(SCN)2·(4 - x) H2O·xTHF phases exhibit a remarkable anisotropic thermal expansion, and Mg(SCN)2·4H2O and Mg(SCN)2·2THF were found to show both positive and negative thermal expansion coefficients.

Probing Charge Accumulation at SrMnO3/SrTiO3 Heterointerfaces via Advanced Electron Microscopy and Spectroscopy.

The last three decades have seen a growing trend toward studying the interfacial phenomena in complex oxide heterostructures. Of particular concern is the charge distribution at interfaces, which is a crucial factor in controlling the interface transport behavior. However, the study of the charge distribution is very challenging due to its small length scale and the intricate structure and chemistry at interfaces. Furthermore, the underlying origin of the interfacial charge distribution has been rarely studied in-depth and is still poorly understood. Here, by a combination of aberration-corrected scanning transmission electron microscopy (STEM) and spectroscopy techniques, we identify the charge accumulation in the SrMnO3 (SMO) side of SrMnO3/SrTiO3 heterointerfaces and find that the charge density attains the maximum of 0.13 ± 0.07 e-/unit cell (uc) at the first SMO monolayer. Based on quantitative atomic-scale STEM analyses and first-principle calculations, we explore the origin of interfacial charge accumulation in terms of epitaxial strain-favored oxygen vacancies, cationic interdiffusion, interfacial charge transfer, and space-charge effects. This study, therefore, provides a comprehensive description of the charge distribution and related mechanisms at the SMO/STO heterointerfaces, which is beneficial for the functionality manipulation via charge engineering at interfaces.

Humidity-Controlled Water Uptake and Conductivities in Ion and Electron Mixed Conducting Polythiophene Films.

Mixed conducting polymer films are of great interest in applications where an interface between electronic and ionic charge transport is needed, e.g., in bioelectronics, electrochemical energy applications, and photovoltaic device interfaces. The role of water on charge transport is of high relevance not only for aqueous environments but also for devices that are manufactured at ambient conditions with varying relative humidities. In this contribution, we present our results on the influence of controlled humidity changes on the mixed conductivity and correlation to the concomitant water uptake in the films. Two sulfonate-bearing polythiophene systems are studied: a self-made conjugated polyelectrolyte, poly(6-(thiophen-3-yl)hexane-1-sulfonate)-sodium (PTS-Na), and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) with different ratios of PEDOT and the polyelectrolyte PSS. Our data give clear evidence of the similarities between the aforementioned polythiophene systems and pure ionic membranes such as Nafion used in fuel cells. As such, a phase separation between the hydrophobic electronically conducting polythiophene phase and the hydrophilic water-swellable ion-conducting phase is proposed. Changing the humidity from dry conditions up to ∼90% relative humidity results in extremely high water uptakes of more than 90 wt %, which corresponds to ∼13 water molecules per sulfonate unit at maximum water uptake. Conversely, the electronic conductivity is less sensitive to increasing humidity, which is due to percolation pathways. The ionic conductivity strongly increases from 10-10 S/cm at dry conditions to 10-3 S/cm at around 30 wt % water content and then levels off at maximum conductivities of 10-3-10-2 S/cm up to water contents of 90 wt %.

Proton uptake in the H(+)-SOFC cathode material Ba(0.5)Sr(0.5)Fe(0.8)Zn(0.2)O(3-δ): transition from hydration to hydrogenation with increasing oxygen partial pressure.

Thermogravimetric investigations on the perovskite Ba(0.5)Sr(0.5)Fe(0.8)Zn(0.2)O(3-δ) (BSFZ, with mixed hole, oxygen vacancy and proton conductivity) from water vapor can occur by acid-base reaction (hydration) or redox reaction (hydrogen uptake), depending on the oxygen partial pressure, i.e. on the material's defect concentrations. In parallel, the effective diffusion coefficient of the stoichiometry relaxation kinetics also changes. These striking observations can be rationalized in terms of a defect chemical model and transport equations for materials with three mobile carriers. Implications for the search of cathode materials with mixed electronic and protonic conductivity for application on proton conducting oxide electrolytes are discussed.

Proton conductivity in mixed-conducting BSFZ perovskite from thermogravimetric relaxation.

The proton conductivity of mixed hole-, oxygen ion- and proton-conducting Ba0.5Sr0.5Fe0.8Zn0.2O3-δ (BSFZ), a potential cathode material for fuel cells based on oxidic proton-conducting electrolytes, was determined from the weight changes of dense pellets upon changing pH2O (and pD2O). The obtained proton concentrations at 20 mbar pH2O range from 1.3 to 0.32 mol% (350-600 °C). The effective diffusion coefficients extracted from the transients and ranging from 1.4 to 29 × 10(-7) cm(2) s(-1) (350 to 600 °C) represent a lower bound for the proton diffusivity and the directly related proton mobility. The calculated proton conductivities reach values in the range of 0.9 to 3 × 10(-4) S cm(-1). Since the real proton conductivity might be underestimated, these values are sufficiently high to render the bulk path in the oxygen reduction mechanism dominant in dense, thin-film electrodes.

Enhanced ionic conductivity in polycrystalline TiO2 by "one-dimensional doping".

The influence of line defects (dislocations) on the electrical properties of polycrystalline TiO2 was investigated. Line defects were created in TiO2 during spark plasma sintering at 1000 °C and 400 MPa. TEM characterisation indicates dislocations to be preferably oriented on {110} and {101} planes. The measured electrical conductivity as a function of oxygen partial pressure and temperature revealed that the dislocations play a vital role in modifying the defect chemistry of TiO2. The presence of dislocations enhanced the ionic conductivity over a wide range of oxygen partial pressures. The observed changes can be interpreted in terms of negatively charged dislocation cores and adjacent space charge accumulation layers. The present findings point towards an alternative method to tune the electrical properties of ionic solids.

Electron and ion transport in Li2O2.

Bulk Li2O2 is shown to exhibit ionic conductivity via lithium vacancies and electronic conductivity via electron holes (localized as superoxide ions). This is the first systematic study on the charge carrier chemistry of peroxides with high relevance for the performance kinetics of Li-oxygen batteries.

Formation and migration of oxygen vacancies in La(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) perovskites: insight from ab initio calculations and comparison with Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ).

The formation and migration of oxygen vacancies in the series of (La,Sr)(Co,Fe)O(3-δ) perovskites, which can be used as mixed conducting SOFC cathode materials and oxygen permeation membranes, are explored in detail by means of first principles density functional calculations. Structure distortions, charge redistributions and transition state energies during the oxygen ion migration are obtained and analyzed. Both the overall chemical composition and vacancy formation energy are found to have only a small impact on the migration barrier; it is rather the local cation configuration which affects the barrier. The electron charge transfer from the migrating O ion towards the transition metal ion in the transition state is much smaller in (La,Sr)(Co,Fe)O(3-δ) compared to (Ba,Sr)(Co,Fe)O(3-δ) perovskites where such a charge transfer makes a significant contribution to the low migration barriers observed (in particular for high Ba and Co content).

Measuring electrical properties of thin film fuel cell electrodes by in situ infrared spectroscopy.

The electrical conductivities of cathode films on a solid oxide fuel cell electrolyte can be determined quantitatively by in situ infrared spectroscopy over a wide range of temperatures and partial oxygen pressures. This method allows measurement of the electrical conductivity of an electrode film on the electrolyte excluding leakage current effects through the substrate.

Fast oxygen exchange kinetics of pore-free Bi(1-x)Sr(x)FeO(3-δ) thin films.

The oxygen incorporation/extraction kinetics of the potential solid oxide fuel cell (SOFC) cathode material Bi(1-x)Sr(x)FeO(3-δ) with x = 0.5 and 0.8 was studied by electrochemical impedance spectroscopy on geometrically well-defined pore-free thin film electrodes. The oxygen exchange rate was found to be higher than that of La(1-x)Sr(x)FeO(3-δ) and-among cobalt-free perovskites-only surpassed by Ba(1-x)Sr(x)FeO(3-δ) which is however known to be unstable in a SOFC environment.

On the proton conductivity in pure and gadolinium doped nanocrystalline cerium oxide.

Conductivity measurements were performed on microcrystalline and nanocrystalline ceria (undoped and doped) in dry as well as wet atmosphere. Below 200-250 °C, the nanocrystalline samples exhibit an enhanced total conductivity under wet conditions, which increases with decreasing temperature. In addition, thermo-gravimetric analysis revealed a strong water uptake below 200 °C. DC-polarization measurements confirm the ionic character of conductivity in the nanocrystalline samples at low temperatures. The role of both grain boundaries and residual porosity on the enhanced conductivity below 200 °C is discussed.

How is oxygen incorporated into oxides? A comprehensive kinetic study of a simple solid-state reaction with SrTiO3 as a model material.

The kinetics of stoichiometry change of an oxide--a prototype of a simple solid-state reaction and a process of substantial technological relevance--is studied and analyzed in great detail. Oxygen incorporation into strontium titanate was chosen as a model process. The complete reaction can be phenomenologically and mechanistically understood beginning with the surface reaction and ending with the transport in the perovskite. Key elements are a detailed knowledge of the defect chemistry of the perovskite as well as the application of a variety of experimental and theoretical tools, many of them evolving from this study. The importance of the reaction and transport steps for (electro)chemical applications is emphasized.

CO2 Selective Potentiometric Sensor in Thick-film Technology.

A potentiometric sensor device based on screen-printed Nasicon films was investigated. In order to transfer the promising sensor concept of an open sodium titanate reference to thick film technology, "sodium-rich" and "sodium-poor" formulations were compared. While the "sodium-rich" composition was found to react with the ion conducting Nasicon during thermal treatment, the "sodium-poor" reference mixture was identified as an appropriate reference composition. Screen-printed sensor devices were prepared and tested with respect to CO2 response, reproducibility, and cross-interference of oxygen. Excellent agreement with the theory was observed. With the integration of a screen-printed heater, sensor elements were operated actively heated in a cold gas stream.

The p(O2) dependence of oxygen surface coverage and exchange current density of mixed conducting oxide electrodes: model considerations.

The charge of adsorbed oxygen species such as O, O or O electrostatically affects the kinetics of the oxygen exchange reaction (1/2O2+2e-<-->O2-) taking place on mixed conducting oxides. For a model assuming a homogeneous double layer of adsorbed ions and counter charges in the mixed conducting electrode it is calculated how the surface coverage theta of the different species depends on the oxygen partial pressure p(O2). Mixed conducting "electron rich" oxides with high electronic carrier concentrations are considered. Models with p(O2) independent hole concentration or p(O2) independent vacancy concentration are discussed as limiting cases. It is quantified how strongly the electrostatic repulsion of adsorbed ions flattens the theta-p(O2) relationships compared to Langmuir's case; even situations can occur in which the surface coverage of some oxygen species decreases with increasing p(O2). In a second step the p(O2)-dependence of the equilibrium exchange rate of the surface reaction 1/2O2+2e-<-->O2- is deduced for several possible rate limiting steps. These relations may serve as a basis for future mechanistic interpretations of the p(O2) dependence of SOFC electrode polarization and of effective surface rate constants kdelta, k* in oxygen stoichiometry change or 18O tracer exchange experiments, respectively.