Interstitial lithium doping in SrTiO3

Strontium titanate (SrTiO3) has received much attention due to its wide range of potential applications including in electrochemical devices such as solid oxide fuel cells and capacitors. The stability and safety features of SrTiO3 led to the development of promising electrodes for Li-ion batteries. Here, we use density functional theory simulations to examine the incorporation of lithium from its gas-phase and bulk forms. The results show that a single Li atom is thermodynamically stable in bulk SrTiO3 with respect to its gas-phase and slightly unfavourable compared to its bulk. Multiple Li incorporation up to six is also considered and the incorporation is exoergic with respect to both gas-phase and bulk forms. Charge analysis confirmed the presence of Li+ ions in the lattice. Li incorporation turns the insulating nature of SrTiO3 into metallic and non-magnetic into magnetic. Lithium incorporation facilitates the formation of Sr, Ti and O vacancies. The loss of Li2O is exoergic suggesting that oxygen vacancy mediated-self diffusion will be promoted

Tailoring the Transport Properties of Mesoporous Doped Cerium Oxide for Energy Applications

Hard-template nanocasted mesoporous cerium oxide possesses a unique combination of thermal stability, high surface area, and short diffusion lengths for mass and gas transport, which makes it relevant for high-temperature catalysis, sensing, and electrochemical applications. Here, we present an in-depth study of a number of mesoporous doped ceria systems, and we assess their fundamental structure and functionalities by complementary transmission electron microscopy imaging and spectroscopy, electron tomography reconstructions, and electrochemical impedance spectroscopy. We employed surface chemical modifications for increasing the ionic conductivity of as-synthesized mesoporous Gd-doped ceria by 2 orders of magnitude, enabling the ionic pathway across mesoporous particles. Complementary bulk doping strategies (by the addition of Pr) result in the easy tuning of the electrical transport mechanisms converting pure ionic mesoporous ceria into a mixed ionic-electronic conductor. The results obtained here are rationalized in light of local charge accumulation and mobility effects, providing a potential tool for engineering transport properties in nanocasted ceria and similar nanostructured materials for use in energy applications in the form of functional composites, infiltrated structures, or catalytic layers

A high-entropy manganite in an ordered nanocomposite for long-term application in solid oxide cells.

The implementation of nano-engineered composite oxides opens up the way towards the development of a novel class of functional materials with enhanced electrochemical properties. Here we report on the realization of vertically aligned nanocomposites of lanthanum strontium manganite and doped ceria with straight applicability as functional layers in high-temperature energy conversion devices. By a detailed analysis using complementary state-of-the-art techniques, which include atom-probe tomography combined with oxygen isotopic exchange, we assess the local structural and electrochemical functionalities and we allow direct observation of local fast oxygen diffusion pathways. The resulting ordered mesostructure, which is characterized by a coherent, dense array of vertical interfaces, shows high electrochemically activity and suppressed dopant segregation. The latter is ascribed to spontaneous cationic intermixing enabling lattice stabilization, according to density functional theory calculations. This work highlights the relevance of local disorder and long-range arrangements for functional oxides nano-engineering and introduces an advanced method for the local analysis of mass transport phenomena

The impact of Mn nonstoichiometry on the oxygen mass transport properties of La0.8Sr0.2MnyO3±δ thin films

Oxygen mass transport in perovskite oxides is relevant for a variety of energy and information technologies. In oxide thin films, cation nonstoichiometry is often found but its impact on the oxygen transport properties is not well understood. Here, we used oxygen isotope exchange depth profile technique coupled with secondary ion mass spectrometry to study oxygen mass transport and the defect compensation mechanism of Mn-deficient La0.8Sr0.2Mn (y) O-3 +/-delta epitaxial thin films. Oxygen diffusivity and surface exchange coefficients were observed to be consistent with literature measurements and to be independent on the degree of Mn deficiency in the layers. Defect chemistry modeling, together with a collection of different experimental techniques, suggests that the Mn-deficiency is mainly compensated by the formation of La-x(Mn) antisite defects. The results highlight the importance of antisite defects in perovskite thin films for mitigating cationic nonstoichiometry effects on oxygen mass transport properties

Control of dopant crystallinity in electrochemically treated cuprate thin films

We present a methodology based on \textit{ex-situ} (post-growth) electrochemistry to control the oxygen concentration in thin films of the superconducting oxide La$_2$CuO$_{4+y}$ grown epitaxially on substrates of isostructural LaSrAlO$_4$. The superconducting transition temperature, which depends on the oxygen concentration, can be tuned by adjusting the pH level of the base solution used for the electrochemical reaction. As our main finding, we demonstrate that the dopant oxygens can either occupy the interstitial layer in an orientationally disordered state or organize into a crystalline phase via a mechanism in which dopant oxygens are inserted into the substrate, changing the lattice symmetry of both the substrate and the epitaxial film. We discuss this mechanism, and describe the resulting methodology as a platform to be explored in thin films of other transition metal oxides.Comment: 10 pages, 4 figure

Solid oxide cell electrode nanocomposites fabricated by inkjet printing infiltration of ceria scaffolds

The enhancement of solid oxide cell (SOC) oxygen electrode performance through the generation of nanocomposite electrodes via infiltration using wet-chemistry processes has been widely studied in recent years. An efficient oxygen electrode consists of a porous backbone and an active catalyst, which should provide ionic conductivity, high catalytic activity and electronic conductivity. Inkjet printing is a versatile additive manufacturing technique, which can be used for reliable and homogeneous functionalization of SOC electrodes via infiltration for either small-or large-area devices. In this study, we implemented the utilization of an inkjet printer for the automatic functionalization of different gadolinium-doped ceria scaffolds, via infiltration with ethanol:water-based La1−xSrxCo1−yFeyO3−δ (LSCF) ink. Scaffolds based on commercial and mesoporous Gd-doped ceria (CGO) powders were used to demonstrate the versatility of inkjet printing as an infiltration technique. Using yttrium-stabilized zirconia (YSZ) commercial electrolytes, symmetrical LSCF/LSCF– CGO/YSZ/LSCF–CGO/LSCF cells were fabricated via infiltration and characterized by SEM-EDX, XRD and EIS. Microstructural analysis demonstrated the feasibility and reproducibility of the process. Electrochemical characterization lead to an ASR value of ≈1.2 Ω cm2 at 750◦C, in the case of nanosized rare earth-doped ceria scaffolds, with the electrode contributing ≈0.18 Ω cm2. These results demonstrate the feasibility of inkjet printing as an infiltration technique for SOC fabrication