Engineering mass transport properties in oxide ionic and mixed ionic electronic thin film ceramic conductors for energy applications

New emerging disciplines such as Nanoionics and Iontronics are dealing with the exploitation of mesoscopic size effects in materials, which become visible (if not predominant) when downsizing the system to the nanoscale. Driven by the worldwide standardisation of thin film deposition techniques, the access to radically different properties than those found in the bulk macroscopic systems can be accomplished. This opens up promising approaches for the development of advanced microdevices, by taking advantage of the nanostructural deviations found in nanometre sized, interface dominated materials compared to the ideal relaxed structure of the bulk. A completely new set of functionalities can be explored, with implications in many different fields such as energy conversion and storage, or information technologies. This manuscript reviews the strategies, employed and foreseen, for engineering mass transport properties in thin film ceramics, with the focus in oxide ionic and mixed ionic electronic conductors and their application in micro power sources

Isotope Exchange Raman Spectroscopy (IERS): a novel technique to probe physicochemical processes inin situsitu

We have developed a novel in situ methodology for the direct study of mass transport properties in oxides with spatial and unprecedented time resolution, based on Raman spectroscopy coupled to isothermal isotope exchanges. Changes in the isotope concentration, resulting in a Raman frequency shift, can be followed in real time, not accessible by conventional methods, enabling complementary insights for the study of ion transport properties of electrode and electrolyte materials for advanced solid-state electrochemical devices. The proof of concept and strengths of isotope exchange Raman spectroscopy (IERS) are demonstrated by studying the oxygen isotope back-exchange in gadolinium-doped ceria (CGO) thin films. Resulting oxygen self-diffusion and surface exchange coefficients are compared to conventional time-of-flight secondary ion mass spectrometry (ToF-SIMS) characterisation and literature values, showing good agreement, while at the same time providing additional insight, challenging established assumptions. IERS captivates through its rapidity, simple setup, non-destructive nature, cost effectiveness and versatile fields of application and thus can readily be integrated as new standard tool for in situ and operando characterization in many laboratories worldwide. The applicability of this method is expected to consolidate our understanding of elementary physicochemical processes and impact various emerging fields including solid oxide cells, battery research and beyond

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

Towards precise defect control in layered oxide structures by using oxide molecular beam epitaxy

In this paper we present the atomic-layer-by-layer oxide molecular beam epitaxy (ALL-oxide MBE) which has been recently installed in the Max-Planck Institute for Solid State Research and we report on its present status, providing some examples that demonstrate its successful application in the synthesis of different layered oxides, with particular reference to superconducting La2CuO4 and insulator-to-metal La2−xSrxNiO4. We briefly review the ALL-oxide MBE technique and its unique capabilities in the deposition of atomically smooth single-crystal thin films of various complex oxides, artificial compounds and heterostructures, introducing our goal of pursuing a deep investigation of such systems with particular emphasis on structural defects, with the aim of tailoring their functional properties by precise defects control

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

Defect energetics in the SrTiO3-LaCrO3 system

Oxide interfaces have attracted a huge amount of interest in recent years due to their novel functionalities that are not possible in bulk. Here we employ atomistic simulation techniques to study the defect properties and oxygen ion migration energy in bulk SrTiO3, LaCrO3 and SrTiO3–LaCrO3 interface. The SrO and La2O3 “Schottky-like” defects are found to be the most favourable intrinsic defects in their respective bulk structures and also at interface layers. While defect energies calculated at interface layers are not significantly changed compared to that calculated in the bulk LaCrO3, significant changes are noted in Schottky defects and oxygen Frenkel between bulk SrTiO3 and the interface. The activation energies for the oxygen ion diffusion in bulk SrTiO3 and LaCrO3 are calculated to be 0.64 eV and 0.53 eV, respectively, suggesting that both materials will present favourable diffusion pathways. In general, there is a reduction in the activation energies of oxygen ion migration at the interface compared to bulk structures. In particular, in the Cr layer, activation energy is calculated to be 0.36 eV implying that interface plays an important role in the oxygen ion migration and therefore such an interface is of interest for use in advanced electrochemical devices

Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3–Ce0.8Sm 0.2O2 Heterointerfaces as All-Ceramic Functional Layers for Solid Oxide Fuel Cell Applications

International audienceThe use of nanostructured interfaces and advanced functional materials opens up a new playground in the field of solid oxide fuel cells. In this work, we present two all-ceramic thin-film heterostructures based on samarium-doped ceria and lanthanum strontium chromite manganite as promising functional layers for electrode application. The films were fabricated by pulsed laser deposition as bilayers or self-assembled intermixed nanocomposites. The microstructural characterization confirmed the formation of dense, well-differentiated, phases and highlighted the presence of strong cation intermixing in the case of the nanocomposite. The electrochemical properties─solid/gas reactivity and in-plane conductivity─are strongly improved for both heterostructures with respect to the single-phase constituents under anodic conditions (up to fivefold decrease of area-specific resistance and 3 orders of magnitude increase of in-plane conductivity with respect to reference single-phase materials). A remarkable electrochemical activity was also observed for the nanocomposite under an oxidizing atmosphere, with no significant decrease in performance after 400 h of thermal aging. This work shows how the implementation of nanostructuring strategies not only can be used to tune the properties of functional films but also results in a synergistic enhancement of the electrochemical performance, surpassing the parent materials and opening the field for the fabrication of high-performance nanostructured functional layers for application in solid oxide fuel cells and symmetric system