A Review of Grain Boundary and Heterointerface Characterization in Polycrystalline Oxides by (Scanning) Transmission Electron Microscopy

Interfaces such as grain boundaries (GBs) and heterointerfaces (HIs) are known to play a crucial role in structure-property relationships of polycrystalline materials. While several methods have been used to characterize such interfaces, advanced transmission electron microscopy (TEM) and scanning TEM (STEM) techniques have proven to be uniquely powerful tools, enabling quantification of atomic structure, electronic structure, chemistry, order/disorder, and point defect distributions below the atomic scale. This review focuses on recent progress in characterization of polycrystalline oxide interfaces using S/TEM techniques including imaging, analytical spectroscopies such as energy dispersive X-ray spectroscopy (EDXS) and electron energy-loss spectroscopy (EELS) and scanning diffraction methods such as precession electron nano diffraction (PEND) and 4D-STEM. First, a brief introduction to interfaces, GBs, HIs, and relevant techniques is given. Then, experimental studies which directly correlate GB/HI S/TEM characterization with measured properties of polycrystalline oxides are presented to both strengthen our understanding of these interfaces, and to demonstrate the instrumental capabilities available in the S/TEM. Finally, existing challenges and future development opportunities are discussed. In summary, this article is prepared as a guide for scientists and engineers interested in learning about, and/or using advanced S/TEM techniques to characterize interfaces in polycrystalline materials, particularly ceramic oxides.

Defect Engineering and Anisotropic Modulation of Ionic Transport in Perovskite Solid Electrolyte LixLa(1−x)/3NbO3

Solid electrolytes, such as perovskite Li3xLa2/1−xTiO3, LixLa(1−x)/3NbO3 and garnet Li7La3Zr2O12 ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in LixLa(1−x)/3NbO3 (x = 0.1 ~ 0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications.

Exploring the Effect of NiO Addition to La0.99Ca0.01NbO4 Proton-Conducting Ceramic Oxides

To improve the performance and overcome the processing difficulties of La0.99Ca0.01NbO4 proton-conducting ceramic oxide, external and internal strategies were used, respectively, to modify La0.99Ca0.01NbO4 with NiO. The external strategy refers to the use of the NiO as a sintering aid. The NiO was added to the synthesized La0.99Ca0.01NbO4 powder as a secondary phase, which is the traditional way of using the NiO sintering aid. The internal strategy refers to the use of NiO as a dopant for the La0.99Ca0.01NbO4. Both strategies improve the sinterability and conductivity, but the effect of internal doping is more significant in enhancing both grain growth and conductivity, making it more desirable for practical applications. Subsequently, the influences of different concentrations of NiO were compared to explore the optimal ratio of the NiO as the dopant. It was found that the sample with 1 or 2 wt.% NiO had similar performance, while with 5 wt.%, NiO doping content hampered the grain growth. In addition, the inhomogeneous distribution of the element in the high-NiO content sample was found to be detrimental to the electrochemical performance, suggesting that the moderate doping strategy is suitable for La0.99Ca0.01NbO4 proton-conducting electrolyte with improved performance. Furthermore, first-principle calculations indicate the origin of the enhanced performance of the internally modified sample, as it lowers both oxygen formation energy and hydration energy compared with the un-modified one, facilitating proton migration.

Piezoelectric nanogenerator based on flexible PDMS-BiMgFeCeO6 composites for sound detection and biomechanical energy harvesting

The piezoelectric nanogenerator (PENG) depends upon the piezoelectric material for the conversion of mechanical stress into useful electrical energy. Development of piezoelectric material compositions starting from ceramic oxides, polymer, and...

Distribution of Characteristic Times: A High-Resolution Spectrum Approach for Visualizing Chemical Relaxation and Resolving Kinetic Parameters of Ionic-Electronic Conducting Ceramic Oxides

Surface exchange coefficient (k) and bulk diffusion coefficient (D) are important properties to evaluate the performance of mixed ionic-electronic conducting (MIEC) ceramic oxides for use in energy conversion devices, such as solid oxide fuel cells. The values of k and D are usually estimated by a non-linear curve fitting procedure based on electrical conductivity relaxation (ECR) measurement. However, the rate-limiting mechanism (or the availability of k and D) and the experimental imperfections (such as flush delay for gaseous composition change, τf) are not reflected explicitly in the time–domain ECR data, and the accuracy of k and D demands a careful sensitivity analysis of the fitting error. Here, the distribution of characteristic times (DCT) converted from time–domain ECR data is proposed to overcome the above challenges. It is demonstrated that, from the DCT spectrum, the rate-limiting mechanism and the effect of τf are easily recognized, and the values of k, D and τf can be determined conjunctly. A strong robustness of determination of k and D is verified using noise-containing ECR data. The DCT spectrum opens up a way towards visible and credible determination of kinetic parameters of MIEC ceramic oxides.