Theoretical and Experimental Insight into the Mechanism for Spontaneous Vertical Growth of ReS2 Nanosheets

Rhenium disulfide (ReS₂) differs fundamentally from other group‐VI transition metal dichalcogenides (TMDs) due to its low structural symmetry, which results in its optical and electrical anisotropy. Although vertical growth is observed in some TMDs under special growth conditions, vertical growth in ReS₂ is very different in that it is highly spontaneous and substrate‐independent. In this study, the mechanism that underpins the thermodynamically favorable vertical growth mode of ReS₂ is uncovered. It is found that the governing mechanism for ReS₂ growth involves two distinct stages. In the first stage, ReS₂ grows parallel to the growth substrate, consistent with conventional TMD growth. However, subsequent vertical growth is nucleated at points on the lattice where Re atoms are “pinched” together. At such sites, an additional Re atom binds with the cluster of pinched Re atoms, leaving an under‐coordinated S atom protruding out of the ReS₂ plane. This under‐coordinated S is “reactive” and binds to free Re and S atoms, initiating growth in a direction perpendicular to the ReS₂ surface. The utility of such vertical ReS₂ arrays in applications where high surface‐to‐volume ratio and electric‐field enhancement are essential, such as surface enhanced Raman spectroscopy, field emission, and solar‐based disinfection of bacteria, is demonstrated.     

Determining the Dielectric Constants of Organic Photovoltaic Materials Using Impedance Spectroscopy

The photovoltaic and electrical properties of organic semiconductors are characterized by their low dielectric constant, which leads to the formation of polarons and Frenkel excitons. The low dielectric constant of organic semiconductors has been suggested to be significantly influential in geminate and bimolecular recombination losses in organic photovoltaics (OPVs). However, despite the critical attention that the dielectric constant has received in literature discussions, there has not yet been a thorough study of the dielectric constant in common organic semiconductors and how it changes when blended. In fact, there have been some inconsistent and contradictory reports on such dielectric constants, making it difficult to identify trends. Herein, at first a detailed explanation of a specific methodology to determine the dielectric constant in OPV materials with impedance spectroscopy is provided, including guidelines for possible experimental pitfalls. Using this methodology, the analysis for the dielectric constant of 17 common neat organic semiconductors is carried out. Furthermore, the relationship between the dielectric constant and blend morphology are studied and determined. It is found that the dielectric constant of a blend system can be very accurately predicted solely based on the dielectric constants of the neat materials, scaled by their respective weight ratios in the blend film.     

Recent Progress in Applications of the Cold Sintering Process for Ceramic–Polymer Composites

Ceramic–polymer composites are of interest for designing enhanced and unique properties. However, the processing temperature windows of sintering ceramics are much higher than that of compaction, extrusion, or sintering of polymers, and thus traditionally there has been an inability to cosinter ceramic–polymer composites in a single step with high amounts of ceramics. The cold sintering process is a low‐temperature sintering technology recently developed for ceramics and ceramic‐based composites. A wide variety of ceramic materials have now been demonstrated to be densified under the cold sintering process and therefore can be all cosintered with polymers from room temperature to 300 °C. Here, the status, understanding, and application of cold cosintering, with different examples of ceramics and polymers, are discussed. One has to note that these types of cold sintering processes are yet new, and a full understanding will only emerge after more ceramic–polymer examples emerge and different research groups build upon these early observations. The general processing, property designs, and an outlook on cold sintering composites are outlined. Ultimately, the cold sintering process could open up a new multimaterial design space and impact the field of ceramic–polymer composites.     

Microstructure Evolution of Concentration Gradient Li[Ni0.75Co0.10Mn0.15]O2 Cathode for Lithium‐Ion Batteries

Detailed analysis of the microstructural changes during lithiation of a full‐concentration‐gradient (FCG) cathode with an average composition of Li[Ni_0.75Co_0.10Mn_0.15]O₂ is performed starting from its hydroxide precursor, FCG [Ni_0.75Co_0.10Mn_0.15](OH)₂ prior to lithiation. Transmission electron microscopy (TEM) reveals that a unique rod‐shaped primary particle morphology and radial crystallographic texture are present in the prelithiation stage. In addition, TEM detected a two‐phase structure consisting of MnOOH and Ni(OH)₂, and crystallographic twins of MnOOH on the Mn‐rich precursor surface. The formation of numerous twins is driven by the lattice mismatch between MnOOH and Ni(OH)₂. Furthermore, the twins persist in the lithiated cathode; however, their density decrease with increasing lithiation temperature. Cation disordering, which influences cathode performance, is observed to continuously decrease with increasing lithiation temperature with a minimum observed at 790 °C. Consequently, lithiation at 790 °C (for 10 h) produced optimal discharge capacity and cycling stability. Above 790 °C, an increase in cation disordering and excessive coarsening of the primary particles lead to the deterioration of electrochemical properties. The twins in the FCG cathode precursor may promote the optimal primary particle morphology by retarding the random coalescence of primary particles during lithiation, effectively preserving both the morphology and crystallographic texture of the precursor.