Phase-Field Based Multiscale Modeling of Heterogeneous Solid Electrolytes: Applications to Nanoporous Li3PS4.

Modeling the effective ion conductivities of heterogeneous solid electrolytes typically involves the use of a computer-generated microstructure consisting of randomly or uniformly oriented fillers in a matrix. However, the structural features of the filler/matrix interface, which critically determine the interface ion conductivity and the microstructure morphology, have not been considered during the microstructure generation. Using nanoporous ß-Li3PS4 electrolyte as an example, we develop a phase-field model that enables generating nanoporous microstructures of different porosities and connectivity patterns based on the depth and the energy of the surface (pore/electrolyte interface), both of which are predicted through density functional theory (DFT) calculations. Room-temperature effective ion conductivities of the generated microstructures are then calculated numerically, using DFT-estimated surface Li-ion conductivity (3.14 × 10-3 S/cm) and experimentally measured bulk Li-ion conductivity (8.93 × 10-7 S/cm) of ß-Li3PS4 as the inputs. We also use the generated microstructures to inform effective medium theories to rapidly predict the effective ion conductivity via analytical calculations. When porosity approaches the percolation threshold, both the numerical and analytical methods predict a significantly enhanced Li-ion conductivity (1.74 × 10-4 S/cm) that is in good agreement with experimental data (1.64 × 10-4 S/cm). The present phase-field based multiscale model is generally applicable to predict both the microstructure patterns and the effective properties of heterogeneous solid electrolytes.

Irradiation Induced Microstructure Evolution in Nanostructured Materials: A Review.

Nanostructured (NS) materials may have different irradiation resistance from their coarse-grained (CG) counterparts. In this review, we focus on the effect of grain boundaries (GBs)/interfaces on irradiation induced microstructure evolution and the irradiation tolerance of NS materials under irradiation. The features of void denuded zones (VDZs) and the unusual behavior of void formation near GBs/interfaces in metals due to the interactions between GBs/interfaces and irradiation-produced point defects are systematically reviewed. Some experimental results and calculation results show that NS materials have enhanced irradiation resistance, due to their extremely small grain sizes and large volume fractions of GBs/interfaces, which could absorb and annihilate the mobile defects produced during irradiation. However, there is also literature reporting reduced irradiation resistance or even amorphization of NS materials at a lower irradiation dose compared with their bulk counterparts, since the GBs are also characterized by excess energy (compared to that of single crystal materials) which could provide a shift in the total free energy that will lead to the amorphization process. The competition of these two effects leads to the different irradiation tolerance of NS materials. The irradiation-induced grain growth is dominated by irradiation temperature, dose, ion flux, character of GBs/interface and nanoprecipitates, although the decrease of grain sizes under irradiation is also observed in some experiments.

Tuning phase stability of complex oxide nanocrystals via conjugation.

Nanocrystals (NCs) attract tremendous research interests because of their unique properties to meet the demands of functionalities. To date, hybrid NCs with multiple components are developed to meet the rising demands that could be very difficult, or even impossible to be achieved by single-component NCs. Tuning properties by strain via conjugation could be an alternative solution. Strain engineering has been discovered and widely applied to many thin-film materials for tuning physical properties. Then, there is a further question to be addressed in this study: can we take the advantages we have learned in heteroepitaxy of thin films and transfer that into the NC conjugation? In order to demonstrate this possibility, we investigated NC conjugation of BiFeO3 and LaAlO3. We found that change in either LaAlO3-NC or BiFeO3-NC size would change the stability of rhombohedral-to-tetragonal phase transition. The present results show that strain engineering is possible to be realized in not only thin film but also NC conjugation. The same concept should be applicable to other complex oxide systems in order to broaden their practical applications for the rising demands of multifunctionalities.