No Arabic abstract
All-solid-state lithium batteries promise significant improvements in energy density and safety over traditional liquid electrolyte batteries. The Al-doped AlxLi7-3xLa3Zr2O12 (LLZO) solid-state electrolyte shows excellent potential given its high ionic conductivity and good thermal, chemical, and electrochemical stability. Nevertheless, further improvements on LLZOs electrochemical and mechanical properties call for an incisive understanding of its local microstructure. Here, we employ Bragg Coherent Diffractive Imaging to investigate the atomic displacements inside single grains of LLZO with various Al-doping concentrations, resulting in cubic, tetragonal, and cubic-tetragonal mixed structures. We observe coexisting domains of different crystallographic orientations in the tetragonal structure. We further show that Al doping leads to crystal defects such as dislocations and phase boundary in the mixed- and cubic-phase grain. This study addresses the effect of Al-doping on the nanoscale structure within individual grains of LLZO, which is informative for the future development of solid-state batteries.
Solid-state electrolytes for Li-ion batteries are attracting growing interest as they allow building safer batteries, also using lithium metal anodes. Here we studied a compound in the lithium superionic conductor (LISICON) family, i.e. Li4-xGe1-xPxO4 (LGPO). Thin films were deposited via pulsed laser deposition and their electrical properties were compared with ceramic pellets. A detailed characterization of the micro structure shows that thin films can be deposited fully crystalline at higher temperatures but also partially amorphous at room temperature. The conductivity is not strongly influenced by the presence of grain boundaries, exposure to air or lithium deficiencies. First-principles molecular dynamics simulations were employed to calculate the lithium ion diffusion profile and the conductivity at various temperatures of the ideal LGPO crystal. Simulations gives the upper limit of conductivity for a defect free crystal, which is in the range of 10-2 S cm-1 at 300 deg. The ease of thin film fabrication, the room-temperature Li-ion conductivity in the range of a few microS cm-1 make LGPO a very appealing electrolyte material for thin film all-solid-state all-oxide microbatteries.
Bulk hexagonal boron nitride (hBN) is a highly nonlinear natural hyperbolic material that attracts major attention in modern nanophotonics applications. However, studies of its optical properties in the visible part of the spectrum and quantum emitters hosted by bulk hBN have not been reported to date. In this work we study the emission properties of hBN crystals in the red spectral range using sub-bandgap optical excitation. Quantum emission from defects is observed at room temperature and characterized in detail. Our results advance the use of hBN in quantum nanophotonics technologies and enhance our fundamental understanding of its optical properties.
By means of Density Functional Theory calculations we evaluate several lithium carbonate - graphite interface models as a prototype of the Solid Electrolyte Interphase capping layer on graphite anodes in lithium-ion batteries. It is found that only an (a,b)-oriented Li2CO3 slab promotes tight binding with graphite. Such mutual organization of the components combines their structural features and reproduces coordination environment of ions, resulting in an adhesive energy of 116 meV/{AA}2 between graphite and lithium carbonate. This model also presents a high potential affinity with bulk. The corresponding charge distribution at such interface induces an electric potential gradient, such a gradient having been experimentally observed. We regard the mentioned criteria as the key descriptors of the interface stability and recommend them as the principal assessments for such interface study. In addition, we evaluate the impact of lithiated graphite on the stability of the model interface and study the generation of different point defects as mediators for Li interface transport. It is found that Li diffusion is mainly provided by interstitials. The induced potential gradient fundamentally assists the intercalation up to lithiation ratio of 70%.
The diffraction technique is widely used in the determination of crystal structures and is one of the bases for the modern science and technology. All related structure determination methods are based on the assumption that perfect single crystal X-ray diffraction (SXRD) can determine a structure uniquely. But as the structure factor phases are lost in SXRD and even more information is lost in powder X-ray diffraction (PXRD), this assumption is still questionable. In this work, we found that structures with certain characteristic can have its sister structure with exactly the same PXRD or even SXRD pattern. A computer program is developed to search the ICSD database, and about 1000 structures were identified to have this characteristic. The original structure and its sister structures can have different space groups, topologies, crystal systems etc. and some may even have multiple sisters. Our studies indicate that special caution is needed since a structure with reasonable atomic positions and perfect match of experimental diffraction intensities could still be wrong.
Control of local lattice perturbations near optically-active defects in semiconductors is a key step to harnessing the potential of solid-state qubits for quantum information science and nanoscale sensing. We report the development of a stroboscopic scanning X-ray diffraction microscopy approach for real-space imaging of dynamic strain used in correlation with microscopic photoluminescence measurements. We demonstrate this technique in 4H-SiC, which hosts long-lifetime room temperature vacancy spin defects. Using nano-focused X-ray photon pulses synchronized to a surface acoustic wave launcher, we achieve an effective time resolution of 100 ps at a 25 nm spatial resolution to map micro-radian dynamic lattice curvatures. The acoustically induced lattice distortions near an engineered scattering structure are correlated with enhanced photoluminescence responses of optically-active SiC quantum defects driven by local piezoelectric effects. These results demonstrate a unique route for directly imaging local strain in nanomechanical structures and quantifying dynamic structure-function relationships in materials under realistic operating conditions.