Progress in Solid State Chemistry最新文献

From crystal chemistry and density functional theory DFT calculations, a stepwise rationale is proposed for the transformation from standalone distorted tetrahedron α-C₅ favored over standalone regular tetrahedron β-C₅ to high density – ultra hard orthorhombic α-C₆ and β-C₆ with qtz (quartz-based) topology characterized by 3D arrangements of distorted tetrahedra to lower density dia-C topology (diamond-like, with regular C4 tetrahedra). Progressive C insertions into orthorhombic α-C₅, α-C₆, and lastly into C₇ were operated leading to ultimate C₈ stoichiometry identified as diamond-like. C₇ was also used as template to devise C₃N₄ carbonitride with exceptional mechanical properties. The induced structural and physical changes are supported with elastic properties pointing to ultra-hardness, larger for qtz α,β-C₆ than dia C₈ and inferred dynamic stability for all stoichiometries from the phonons band structures. The thermodynamic quantities as the specific heat were compared with diamond experimental C_V. The electronic band structures reveal semi-conducting C₆, metallic C₇ characterized by diamond-defect structure, and insulating C₈. The results are meant to help further systemic understanding of tetrahedral carbon allotropes.

Interest in perovskite solar cell (PSC) research is increasing because PSC has a remarkable power conversion efficiency (PCE), which has notably risen to 28.3 %. However, commercialization of PSCs faces a significant obstacle due to their stability issues. This review article primarily focuses on several key aspects of PSCs, including different types of solar cells, their construction and operational mechanisms, efficiency, and overall stability. It explains the structure and functioning of PSCs, covering materials and components used for absorber layer, electron-transport layer, hole-transport layer, and electrodes. This review emphasized stability challenges associated with PSCs and discussed various factors and issues contributing to the degradation of these solar cells over time. It then provided a concise overview of different strategies and ongoing efforts taken to enhance the stability of PSCs. It also summarized various approaches used to improve their durability. In summary, this article offers a comprehensive exploration of PSCs, encompassing their construction, operation, improvement in efficiency, and obstacles related to their long-term stability. Furthermore, it addresses factors influencing PSC stability and outlines future challenges, focusing on prolonging their lifespan and enhancing stability for broader applications. Finally, this article has tackled various possible solutions to address the challenges encountered by the PSCs.

Fe³⁺-activated near-infrared (NIR) luminescent materials have attracted growing research interests for their tunable broadband emission and extensive application potentials in the fields of night vision, biomedical imaging, nondestructive food analysis, etc. Deep insight into the relation between crystal structure and luminescence performance plays a significant role in developing novel efficient NIR functional materials. In this review, after a brief introduction, we first discuss the mechanism of Fe³⁺ luminescence in octahedral and tetrahedral crystal fields based on the Tanabe-Sugano energy level diagram. Next, the research progress of Fe³⁺-doped NIR luminescent materials, including structure, property and potential application, is summarized, followed by the strategies to enhance NIR steady-state luminescence, persistent luminescence and mechanoluminescence performances. Then we conduct a comparison of luminescence efficiency and luminescence thermal stability of Fe³⁺-doped NIR materials. At last, we propose several challenges and outlooks in the research of Fe³⁺-activated NIR luminescent materials. This review is aimed to provide a deeper understanding of not only Fe³⁺ luminescence mechanism but also the current research progress of Fe³⁺-doped materials, so as to provide constructive strategy in the exploitation of efficient Fe³⁺-activated NIR luminescent materials.

This review presents an overview on the structures and electrical properties of B-site deficient hexagonal perovskite oxides, which have been receiving increasing attention as key components as dielectric resonators in microwave telecommunications, as well as solid-state oxide ion and proton conductors in solid oxide fuel cells. The structural evolution and stability, order-disorder of cation and anions, and mechanisms underlying the dielectric and ionic conduction behaviors for the B-site deficient hexagonal perovskites are summarized and the roles of the B-site deficiency on the structural stability and option, ion order-disorder and electrical performance are highlighted. This provides useful guidance for design of new hexagonal perovskite oxide materials and structural control to enhance their electrical properties and discover new functionality as dielectric resonators and solid-state ionic conductors.

The undesirable capacity degradation of LiMnPO₄ upon cycling at high temperatures is a challenge to its practical application. Herein, a lattice doping strategy is adopted to improve the high-temperature cycling stability of LiMnPO₄, and the comparative study reveals that Al³⁺ doping into LiMnPO₄ in a form of Li_0.98Al_0.02MnPO₄ is highly beneficial to the cycling performance of LiMnPO₄ and the capacity retention can be significantly improved from 67.4 % to 93.4 % after 100 cycles at 1C at 60 °C, because Al³⁺ doping can effectively reduce passivation products deposition on the cathode and manganese dissolution in the electrolyte, which thus improve the cathode/electrolyte interface and stabilize the structure of LiMnPO₄ at high temperatures.

Chromophores at different coordinations can give rise to different colors; usually, chromophores at non-centrosymmetric coordinations are preferred for intense pigments. Different solid solutions M_2-xCo_xM’O₄ (M = Mg/Zn, and M’ = Ti/Sn) with inverse spinel structure were synthesized with the goal of understanding color variation with site distribution, as the chromophore Co²⁺ in these solid solutions can occupy either the tetrahedral or octahedral sites or both depending on the composition. Another goal was to develop environmentally friendly and cheap blue pigments by reducing the carcinogenic cobalt to obtain a similar color to that of commercially available cobalt blue, which uses a significant amount of Co²⁺ (33.31 % by mass). For Mg_2-xCo_xTiO₄ series, turquoise blue hues were observed for low cobalt content, and different shades of blue were observed for Mg_2-xCo_xSnO₄ series with a color similar to cobalt blue, including just 4.90% of cobalt by mass. While for Zn_2-xCo_xTiO₄, and Zn_2-xCo_xSnO₄ series, different shades of brown and different shades of green, respectively, were observed. One of the main reasons behind the major difference in color for the Mg and Zn containing solid solutions, regardless of the same chromophore in the same structure is related to the chromophore site distribution in the system. For the Mg-containing solid solutions, different shades of blue are observed as Mg has no preference for any of the sites, Co²⁺ mostly goes to tetrahedral sites. In contrast, for the Zn-containing solid solutions, no blue shades were observed because of the strong preference of Zn for the tetrahedral sites owing to the sp³ hybridization, which in turn forces Co²⁺ to occupy the octahedral sites. Neutron refinement proves that Co²⁺ occupies mainly tetrahedral sites in the Mg-containing solid solutions and mostly octahedral sites in the Zn-containing solid solutions.

The primary objective of this study is to explore the relationship between the composition, structure, and thermal characteristics of M-Al-Si-O-N glasses, with M representing sodium (Na), magnesium (Mg), or calcium (Ca). The glasses were prepared by melting in a quartz crucible at 1650 °C and AlN precursor (powder) was utilized as a nitrogen source. The measured thermal properties studied were glass transition temperature (T_g), crystallization temperature (T_c), glass stability, viscosity, and thermal expansion coefficient (α). The findings indicate that increasing the aluminum content leads to higher glass transition, crystallization temperatures, and viscosities. In contrast, fragility values increase with the Al contents, while modifier elements and silicon content influence thermal expansion coefficient values. FTIR analysis revealed that in all glasses, the dominant IR bands are attributed to the presence of Q² and Q³ silicate units. The effect of Al is observed as a progressive polymerization of the silicate network resulting from the glass-forming role of Al₂O₃. In most samples, the Q⁴ silicate mode was also observed, strongly related to the high Al content. Overall, the study shows that the complexity of composition-property correlations where the structural changes affect the properties of Mg/Ca-based oxynitride glasses has potential implications for their use in various technological fields.

Infrared nonlinear optical (IR-NLO) crystals with excellent properties are in extensive demand due to their important role in IR laser technology. Currently, it remains a great challenge to obtain IR-NLO materials with both high second harmonic generation (SHG) response and large laser-induced damage thresholds (LIDTs). Some structural design strategies such as ‘structural/functional regions’ have been adopted to develop new high-performance NLO materials. The covalent structural region producing SHG signals has been extensively investigated, whereas the hard cations (alkali, alkaline-earth, and rare-earth metal ions) which are responsible for improving LIDTs, have been relatively neglected. Utilizing the concept of structural/functional regions, we focus on the relation between structural regions and SHG properties in chalcogenides. Combining different kinds of hard cations can change the dimension of structures and affect the stacking of NLO-active groups. Introducing more hard cations and constructing more complex ion regions help to increase the laser damage threshold. Based on the mentioned structural strategies, guidance will be provided for developing high-performance multiple-cation materials for IR NLO applications.

With the increasing maturity of lithium-ion battery (LIB) research and large-scale commercial application, the shortage of lithium resources has gradually emerged. Sodium-ion batteries (SIB) have become a potential choice for secondary battery energy storage systems due to their abundant resources, high efficiency, and ease of use. The cathode materials of sodium-ion batteries affect the key performance of batteries, such as energy density, cycling performance, and rate characteristics. At present, transition metal oxides, polyanion compounds, and Prussian blue compounds have been reported as cathode materials. This paper summarizes the classification, performance characteristics, and research progress of main cathode materials for sodium-ion batteries, and prospects the potential research directions.

The present study aims to describe the role of the grain size on the properties of submicron- and nano-structured Ba_0·8Sr_0·2TiO₃ (BST) ceramics. Dense (1 − 2% porosity) ceramics with average grain sizes in the range of (77 − 234) nm were consolidated under different spark plasma sintering conditions starting from nanopowders with a mean particle size of 70 nm, synthesized via the acetate variant of the sol-gel method. The structural analysis based on XRD data revealed a mixture of cubic and tetragonal modifications at room temperature for the precursor powders and for all the investigated ceramics. The structural heterogeneity of the individual ceramic grains with coexistence of cubic and tetragonal polymorphs was confirmed by HR-TEM investigations. Accordingly, a “brick-wall" model with cubic grain boundary regions and tetragonal grain cores is proposed. By increasing the grain size, from 77 to 234 nm, a decrease of the phase transitions diffuseness accompanied by an increase of the permittivity maxima (from 650 to 4500) and dielectric losses (from 5 to 7.5%, at 100 Hz), was detected by broadband dielectric spectroscopy. No variation of the Curie temperature in the investigated Ba_0·8Sr_0·2TiO₃ ceramics was detected, unlike typically reported for BaTiO₃ ceramics with similar grain sizes. The Curie-Weiss temperature and the Curie constant decrease when grain size is diminished, indicating an overall reduction of the ferroelectric active volume, as a scaling effect. The ferroelectric switching was demonstrated for all the selected fine-grained BST ceramics, either at nanoscale or macroscopically, with an increased ferroelectric character for the coarser submicron-structured ceramics, with respect to the nanocrystalline one. The observed properties of the fine-grained Ba_0·8Sr_0·2TiO₃ ceramics are explained in the frame of multiphase coexistence and ferroelectricity “dilution” due to the increasing role of non-ferroelectric grain boundaries when reducing grain size and complete the knowledge on the scale-dependent properties of dense fine-grained BaTiO₃-based ceramics.