ABSTRACT
Aqueous aluminum ion batteries (AAIBs) hold significant potential for grid-scale energy storage owing to their intrinsic safety, high theoretical capacity, and abundance of aluminum. However, the strong electrostatic interactions and delayed charge compensation between high-charge-density aluminum ions and the fixed lattice in conventional cathodes impede the development of high-performance AAIBs. To address this issue, this work introduces, for the first time, high-entropy Prussian blue analogs (HEPBAs) as cathodes in AAIBs with unique lattice tolerance and efficient multipath electron transfer. Benefiting from the intrinsic long-range disorder and robust lattice strain field, HEPBAs enable the manifestation of the lattice respiration effect and minimize lattice volume changes, thereby achieving one of the best long-term stabilities (91.2% capacity retention after 10 000 cycles at 5.0 A g-1) in AAIBs. Additionally, the interaction between the diverse metal atoms generates a broadened d-band and reduced degeneracy compared with conventional Prussian blue and its analogs (PBAs), which enhances the electron transfer efficiency with one of the best rate performance (79.2 mAh g-1 at 5.0 A g-1) in AAIBs. Furthermore, exceptional element selectivity in HEPBAs with unique cocktail effect can facile tune electrochemical behavior. Overall, the newly developed HEPBAs with a high-entropy effect exhibit promising solutions for advancing AAIBs and multivalent-ion batteries.
ABSTRACT
The sintering of osmium is critical for the preparation of raw material targets for film coating, which is the main application area of osmium. In order to get a better understanding of the intrinsic mechanism of densification of osmium, a serial study on the sintering behavior of osmium has been made in this study. By the master sintering curve (MSC) and constant heating rate (CHR) method, the sintering activation energy of nanosized osmium is evaluated to be about 340 kJ/mol, which is higher than most other metals. The density-functional theory calculation indicates the higher energy barrier of the surface atom and vacancy migration and lacking migration tunnel of inner point vacancies. For example, the diffusion of osmium atoms on the surface of particles is mainly limited by Os (1010), which has an energy barrier as high as 1.14 eV, that is higher than the W atom on W (110) of 0.99 eV. The vacancy migration energy barrier inside osmium's grains is higher than 3.0 eV, while that of W is only 1.7 eV. This means that it is more difficult for osmium to achieve a high density compared with W, which is consistent with the experimental results. Accordingly, the proposed strategy provides a new opportunity to design a sintering process for target fabrication with excellent properties for various applications.
ABSTRACT
The light-emitting diodes (LED) are regarded as one of the most promising devices for inexpensive and widely used illumination; in particular, they are highly dependent on the development of red-emitting phosphors. Herein, we developed two types of red-emitting (Ba, Ca)2ScAlO5:Eu3+ multiple excitations phosphors (λex = 255-465 nm) via freeze-drying followed by calcination. Powder X-ray diffraction and NMR results point out that they have hexagonal space group P63/mmc (194), and the structural framework is composed of multi-coordinated Al3+-O2- polyhedron and Sc3+-O2- polyhedron. In addition, the valence state of europium (Eu3+) is confirmed by X-ray photoelectron spectroscopy characterization. Investigation on the photoluminescence properties showed that the photoluminescence process of (Ba, Ca)2ScAlO5:Eu3+ is attributable to the charge transfer band of Eu-O and abundant spectral terms of Eu3+. The α-(Ba, Ca)2ScAlO5:Eu3+ and ß-(Ba, Ca)2ScAlO5:Eu3+ exhibited red emission under 465 and 395 nm excitation, respectively. The PL spectra and decay curves explain the intrinsic photoluminescence mechanism. The strongest emission peaks of the red-emitting α-(Ba, Ca)2ScAlO5:Eu3+ and ß-(Ba, Ca)2ScAlO5:Eu3+ phosphors are at 615 and 619 nm, respectively, exhibiting a high fluorescence of 64 and 67% under the temperature of 423 K (150 °C). Further exploration of the red-emitting phosphors would provide a variety of choices for the design of red LEDs and white LEDs for the solid-state lighting system.
