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The dissolution of intermediate lithium polysulfides (LiPS) into an electrolyte and their shuttling between the electrodes have been the primary bottlenecks for the commercialization of high-energy density lithium-sulfur (Li-S) batteries. While several two-dimensional (2D) materials have been deployed in recent years to mitigate these issues, their activity is strictly restricted to their edge-plane-based active sites. Herein, for the first time, we have explored a phase transformation phenomenon in a 2D material to enhance the number of active sites and electrocatalytic activity toward LiPS redox reactions. Detailed theoretical calculations demonstrate that phase transformation from the 2H to 1T' phase in a MoSe2 material activates the basal planes that allow for LiPS adsorption. The corresponding transformation mechanism and LiPS adsorption capabilities of the as-formed 1T'-MoSe2 were elucidated experimentally using microscopic and spectroscopic techniques. Further, the electrochemical evaluation of phase-transformed MoSe2 revealed its strong electrocatalytic activity toward LiPS reduction and their oxidation reactions. The 1T'-MoSe2-based cathode hosts for sulfur later provide a superior cycling performance of over 250 cycles with a capacity loss of only 0.15% per cycle along with an excellent Coulombic efficiency of 99.6%.
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Mixed cationic and anionic redox cathode chemistry is emerging as the conventional cationic redox centers of transition-metal-based layered oxides are reaching their theoretical capacity limit. However, these anionic redox reactions in transition metal oxide-based cathodes attained by taking excess lithium ions have resulted in stability issues due to weak metal-oxygen ligand covalency. Here, we present an alternative approach of improving metal-ligand covalency by introducing a less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal d band penetrates into the ligand p band, thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report the possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe2+/3+ are introduced in the Li-ion conducting phase (Li2SnS3). Further, the electron energy loss spectroscopy and X-ray absorption near-edge structure analyses are used to qualitatively identify the charge contributors at the metal and ligand sites during Li+ extraction. The detailed high-resolution transmission electron microscopy and high annular dark field-scanning transmission electron microscopy investigations reveal the multi-redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen-based dual anionic and cationic redox cathode avenue.
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We synthesized Co2P nanoparticle encapsulated N-doped carbon nanocages through one-step carbonization-phosphidation of ZIF-67. As potassium ion battery (KIB, PIB) anodes, the Co2P@NCCs display state-of-the-art electrochemical performance, including the most favorable fast charge characteristics reported. The single-nanometer thick carbon cage yields rapid solid-state K-ion diffusion and prevents aggregation/pulverization of 40 nm cobalt phosphide.
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We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. It also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core-shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na2Se2 (hcp) and Na2Se (fcc). A nanoscale fracture of terminally sodiated Na-Se is observed by HAADF, with SSNMR, indicating a physical separation of some Se from the carbon host after the first cycle. GITT reveals a 3-fold increase in Na+ diffusivity at cycle 2, which may be explained by the creation of extra interfaces. These combined findings highlight the complex phenomenology of electrochemical phase transformations in nanoconfined materials, which may profoundly differ from their "free" counterparts.
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INTRODUCTION: Abdominal wall hernias through the arcuate line termed Spigelian hernias are uncommon. These hernias presenting as a Richter-type, with strangulation of part of the circumference of the bowel wall is very rare. PRESENTATION OF CASE: We report a 27-year-old male patient who presented with a Richter-type Spigelian hernia. LITERATURE REVIEW: A MEDLINE literature search of this rare entity yielded six publications presenting Richter-type Spigelian hernias. All of these articles and accompanying references were thoroughly reviewed. There was no gender or anatomical side predominance among the patients. All except our patient presented here were elderly. Pain was the most common symptom and was present in all patients. All patients underwent surgical repair and none reported recurrence of their hernia afterwards. DISCUSSION AND CONCLUSION: Richter-type Spigelian hernia is rare and has been reported infrequently in the existing literature. Clinical diagnosis is challenging and CT scan is the diagnostic study of choice. Surgical repair is the definitive treatment and involves primary or mesh repair of the defect as appropriate. Necrotic bowel should be resected and we recommend biologic mesh repair in these cases if the defect is large.
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Inflammatory pseudotumors, now more aptly termed inflammatory myofibroblastic tumors (IMTs), are uncommon benign neoplasms, which have been reported in most organs and tissues in the body. Originally described and commonly found in the lung, they are also found in the liver of children and adults. We review the literature and analyze the features of the hepatic IMTs reported in children, along with a case report of a 15-month-old boy who had a persistent IMT in the liver and underwent surgical resection for the same following a trial of conservative management.