Challenges for density functional theory in simulating metal-metal singlet bonding: A case study of dimerized VO2.

VO2 is renowned for its electric transition from an insulating monoclinic (M1) phase, characterized by V-V dimerized structures, to a metallic rutile (R) phase above 340 K. This transition is accompanied by a magnetic change: the M1 phase exhibits a non-magnetic spin-singlet state, while the R phase exhibits a state with local magnetic moments. Simultaneous simulation of the structural, electric, and magnetic properties of this compound is of fundamental importance, but the M1 phase alone has posed a significant challenge to the density functional theory (DFT). In this study, we show none of the commonly used DFT functionals, including those combined with on-site Hubbard U to treat 3d electrons better, can accurately predict the V-V dimer length. The spin-restricted method tends to overestimate the strength of the V-V bonds, resulting in a small V-V bond length. Conversely, the spin-symmetry-breaking method exhibits the opposite trends. Each of these two bond-calculation methods underscores one of the two contentious mechanisms, i.e., Peierls lattice distortion or Mott localization due to electron-electron repulsion, involved in the metal-insulator transition in VO2. To elucidate the challenges encountered in DFT, we also employ an effective Hamiltonian that integrates one-dimensional magnetic sites, thereby revealing the inherent difficulties linked with the DFT computations.

Dual carbon engineering enabling 1T/2H MoS2 with ultrastable potassium ion storage performance.

Potassium-ion batteries (PIBs) as a promising and low-cost battery technology offer the advantage of utilizing abundant and cost-effective K-salt sources. However, the effective adoption of PIBs necessitates the identification of suitable electrode materials. The 1T phase of MoS2 exhibits enhanced electronic conductivity and greater interlayer spacing compared to the 2H phase, leading to a capable potassium ion storage ability. Herein, we fabricated dual carbon engineered 1T/2H MoS2via a secure and straightforward ammonia-assisted hydrothermal method. The 1T/2H MoS2@rGO@C structure demonstrated an expanded interlayer spacing (9.3 Å). Additionally, the sandwich-like structural design not only enhanced material conductivity but also effectively curbed the agglomeration of nanosheets. Remarkably, 1T/2H MoS2@rGO@C exhibited impressive potassium storage ability, delivering capacities of 351.0 mA h g-1 at 100 mA g-1 and 233.8 mA h g-1 at 1000 mA g-1 following 100 and 1000 cycles, respectively. Moreover, the construction of a K-ion full cell was successfully achieved, utilizing perylene tetracarboxylic dianhydride (PTCDA) as the cathode, and manifesting a capacity of 294.3 mA h g-1 at 100 mA g-1 after 160 cycles. This underscores the substantial potential of employing the 1T/2H MoS2@rGO@C electrode material for PIBs.

Engineering contact curved interface with high-electronic-state active sites for high-performance potassium-ion batteries.

Potassium-ion batteries (PIBs) have attracted ever-increasing interest due to the abundant potassium resources and low cost, which are considered a sustainable energy storage technology. However, the graphite anodes employed in PIBs suffer from low capacity and sluggish reaction kinetics caused by the large radius of potassium ions. Herein, we report nitrogen-doped, defect-rich hollow carbon nanospheres with contact curved interfaces (CCIs) on carbon nanotubes (CNTs), namely CCI-CNS/CNT, to boost both electron transfer and potassium-ion adsorption. Density functional theory calculations validate that engineering CCIs significantly augments the electronic state near the Fermi level, thus promoting electron transfer. In addition, the CCIs exhibit a pronounced affinity for potassium ions, promoting their adsorption and subsequently benefiting potassium storage. As a result, the rationally designed CCI-CNS/CNT anode shows remarkable cyclic stability and rate capability. This work provides a strategy for enhancing the potassium storage performance of carbonaceous materials through CCI engineering, which can be further extended to other battery systems.

Wide-Temperature Operation of Lithium-Sulfur Batteries Enabled by Multi-Branched Vanadium Nitride Electrocatalyst.

High-performance lithium-sulfur (Li-S) batteries that can work normally under harsh conditions have attracted tremendous attention; however, the sluggish reaction kinetics of polysulfide conversions at low temperatures as well as the notorious polysulfide shuttling at high temperatures remain to be resolved. Herein, a multibranched vanadium nitride (MB-VN) electrocatalyst has been designed and deployed for Li-S batteries. Both experimental (time-of-flight secondary ion mass spectroscopy and adsorption tests) and theoretical results verify the strong chemical adsorption capability and high electrocatalytic activity of MB-VN with respect to polysulfides. Moreover, in situ Raman characterization manifests the effective inhibition of polysulfide shuttling by the MB-VN electrocatalyst. Using MB-VN-modified separators, the Li-S batteries deliver an excellent rate capability (707 mAh g-1 at 3.0 C) and great cyclic stability (678 mAh g-1 after 400 cycles at 1.0 C) at room temperature. With 6.0 mg cm-2 of sulfur and a lean electrolyte volume of ∼6 µL mgs-1, Li-S batteries exhibit a high areal capacity of 5.47 mAh cm-2. Even over a wide temperature range (-20 to +60 °C), the Li-S batteries still maintain stable cyclic performance at high current rates. This work demonstrates that metal nitride based electrocatalysts can realize low-/high-temperature-tolerant Li-S batteries.

Association of Tirofiban With Functional Outcomes After Thrombectomy in Acute Ischemic Stroke Due to Intracranial Atherosclerotic Disease.

BACKGROUND AND OBJECTIVE: To investigate the efficacy and safety of IV infusion of tirofiban before endovascular thrombectomy for patients with large vessel occlusion due to intracranial atherosclerotic disease. The secondary objective was to identify potential mediators for the clinical effect of tirofiban. METHODS: Post hoc exploratory analysis of the Endovascular Treatment With versus Without Tirofiban for Patients with Large Vessel Occlusion Stroke (RESCUE BT) trial, which was a randomized, double-blinded, placebo-controlled trial at 55 centers in China from October 2018 to October 2021. Patients with occlusion of the internal carotid artery or middle cerebral artery due to intracranial atherosclerosis were included. The primary efficacy outcome was the proportion of patients achieving functional independence (defined as modified Rankin scale 0-2) at 90 days. Binary logistic regression and causal mediation analyses were used to estimate the treatment effect of tirofiban and the potential mediators. RESULTS: This study included 435 patients, of whom 71.5% were men. The median age was 65 (interquartile range [IQR] 56-72) years, with a median NIH Stroke Scale of 14 (IQR 10-19). Patients in the tirofiban group had higher rates of functional independence at 90 days than patients in the placebo group (adjusted odds ratio 1.68; 95% CI 1.11-2.56, p = 0.02) without an increased risk of mortality or symptomatic intracranial hemorrhage. Tirofiban was associated with fewer thrombectomy passes (median [IQR] 1 [1-2] vs 1 [1-2], p = 0.004), which was an independent predictor of functional independence. Mediation analysis showed tirofiban-reduced thrombectomy passes explained 20.0% (95% CI 4.1%-76.0%) of the effect of tirofiban on functional independence. DISCUSSION: In this post hoc analysis of the RESCUE BT trial, tirofiban was an effective and well-tolerated adjuvant medication of endovascular thrombectomy for patients with large vessel occlusion due to intracranial atherosclerosis. These findings need to be confirmed in future trials. TRIAL REGISTRATION INFORMATION: The RESCUE BT trial was registered on the Chinese Clinical Trial Registry: chictr.org.cn, ChiCTR-INR-17014167. CLASSIFICATION OF EVIDENCE: This study provides Class II evidence that tirofiban plus endovascular therapy improves 90-day outcome for patients with large vessel occlusion due to intracranial atherosclerosis.

Electrospun carbon-based nanomaterials for next-generation potassium batteries.

Rechargeable potassium (K) batteries that are of low cost, with high energy densities and long cycle lives have attracted tremendous interest in affordable and large-scale energy storage. However, the large size of the K-ion leads to sluggish reaction kinetics and causes a large volume variation during the ion insertion/extraction processes, thus hindering the utilization of active electrode materials, triggering a serious structural collapse, and deteriorating the cycling performance. Therefore, the exploration of suitable materials/hosts that can reversibly and sustainably accommodate K-ions and host K metals are urgently needed. Electrospun carbon-based materials have been extensively studied as electrode/host materials for rechargeable K batteries owing to their designable structures, tunable composition, hierarchical pores, high conductivity, large surface areas, and good flexibility. Here, we present the recent developments in electrospun CNF-based nanomaterials for various K batteries (e.g., K-ion batteries, K metal batteries, K-chalcogen batteries), including their fabrication methods, structural modulation, and electrochemical performance. This Feature Article is expected to offer guidelines for the rational design of novel electrospun electrodes for the next-generation K batteries.

Twenty-four-hour National Institute of Health Stroke Scale predicts short- and long-term outcomes of basilar artery occlusion after endovascular treatment.

Background: The present study aimed to evaluate the prognostic value of the 24-h National Institute of Health Stroke Scale (NIHSS) for short- and long-term outcomes of patients with basilar artery occlusion (BAO) after endovascular treatment (EVT) in daily clinical routine. Methods: Patients with EVT for acute basilar artery occlusion study registry with the 24-h NIHSS, and clinical outcomes documented at 90 days and 1 year were included. The NIHSS admission, 24-h NIHSS, NIHSS delta, and NIHSS percentage change, binary definitions of early neurological improvement [ENI; improvement of 4/(common ENI)/8 (major ENI)/10 (dramatic ENI)] NIHSS points were compared to predict the favorable outcomes and mortality at 90 days and 1 year. The primary outcome was defined as favorable if the modified Rankin Scale (mRS) score was 0-3 at 90 days. Results: Of the 644 patients treated with EVT, the 24-h NIHSS had the highest discriminative ability for favorable outcome prediction [receiver operator characteristic (ROC)NIHSS 24 h area under the curve (AUC): 0.92 (0.90-0.94)] at 90 days and 1 year [(ROCNIHSS 24 h AUC: 0.91 (0.89-0.94)] in comparison to the NIHSS score at admission [ROCNIHSS admission AUC at 90 days: 0.73 (0.69-0.77); 1 year: 0.74 (0.70-0.78)], NIHSS delta [ROCΔ NIHSS AUC at 90 days: 0.84 (0.81-0.87); 1 year: 0.81 (0.77-0.84)], and NIHSS percentage change [ROC%change AUC at 90 days: 0.85 (0.82-0.89); 1 year: 0.82 (0.78-0.86)]. Conclusion: The 24-h NIHSS with a threshold of ≤23 points was the best surrogate for short- and long-term outcomes after EVT for BAO in the clinical routine.

Effect of Intravenous Tirofiban vs Placebo Before Endovascular Thrombectomy on Functional Outcomes in Large Vessel Occlusion Stroke: The RESCUE BT Randomized Clinical Trial.

Importance: Tirofiban is a highly selective nonpeptide antagonist of glycoprotein IIb/IIIa receptor, which reversibly inhibits platelet aggregation. It remains uncertain whether intravenous tirofiban is effective to improve functional outcomes for patients with large vessel occlusion ischemic stroke undergoing endovascular thrombectomy. Objective: To assess the efficacy and adverse events of intravenous tirofiban before endovascular thrombectomy for acute ischemic stroke secondary to large vessel occlusion. Design, Setting, and Participants: This investigator-initiated, randomized, double-blind, placebo-controlled trial was implemented at 55 hospitals in China, enrolling 948 patients with stroke and proximal intracranial large vessel occlusion presenting within 24 hours of time last known well. Recruitment took place between October 10, 2018, and October 31, 2021, with final follow-up on January 15, 2022. Interventions: Participants received intravenous tirofiban (n = 463) or placebo (n = 485) prior to endovascular thrombectomy. Main Outcomes and Measures: The primary outcome was disability level at 90 days as measured by overall distribution of the modified Rankin Scale scores from 0 (no symptoms) to 6 (death). The primary safety outcome was the incidence of symptomatic intracranial hemorrhage within 48 hours. Results: Among 948 patients randomized (mean age, 67 years; 391 [41.2%] women), 948 (100%) completed the trial. The median (IQR) 90-day modified Rankin Scale score in the tirofiban group vs placebo group was 3 (1-4) vs 3 (1-4). The adjusted common odds ratio for a lower level of disability with tirofiban vs placebo was 1.08 (95% CI, 0.86-1.36). Incidence of symptomatic intracranial hemorrhage was 9.7% in the tirofiban group vs 6.4% in the placebo group (difference, 3.3% [95% CI, -0.2% to 6.8%]). Conclusions and Relevance: Among patients with large vessel occlusion acute ischemic stroke undergoing endovascular thrombectomy, treatment with intravenous tirofiban, compared with placebo, before endovascular therapy resulted in no significant difference in disability severity at 90 days. The findings do not support use of intravenous tirofiban before endovascular thrombectomy for acute ischemic stroke. Trial Registration: Chinese Clinical Trial Registry Identifier: ChiCTR-IOR-17014167.

Impact of Body Temperature in Patients With Acute Basilar Artery Occlusion: Analysis of the BASILAR Database.

Background: A link between body temperature and stroke outcomes has been established but not for acute basilar artery occlusion. We aimed to determine the association between body temperature and clinical outcomes in patients with acute basilar artery occlusion and temperature management range. Methods: We included patients from the Endovascular Treatment for Acute Basilar Artery Occlusion Study (BASILAR) database with records of both admission body temperature (ABT) and peak body temperature (PBT). ABT was defined as the body temperature first measured at the hospital visit, PBT was defined as the highest temperature within 24 h of treatment, and minus body temperature (MBT) was defined as PBT-ABT. The primary clinical outcome was favorable functional outcome, defined as the proportion of patients with a modified Rankin Scale score of 0-3 at 3 months. Secondary outcomes included 3-month mortality, in-hospital mortality, and symptomatic cerebral hemorrhage. Results: A total of 664 patients were enrolled in the study; 74.7% were men, with a median age of 65 (interquartile range, 57.25-74) years. In all patients, multivariate analysis indicated that PBT and MBT were independent predictors of favorable functional outcome [odds ratio (OR), 0.57 (95% CI, 0.43-0.77); OR, 0.68 (95% CI, 0.52-0.88), respectively], and higher ABT, PBT, and MBT were associated with an increased 3-month mortality [OR, 1.47 (95% CI, 1.03-2.10), OR, 1.58 (95% CI, 1.28-1.96), OR, 1.35 (95% CI, 1.11-1.65), respectively]. Proportional odds models demonstrated that when ABT, PBT, MBT were in the range of <37.5, <38.9, and -0.6-2.7°C, respectively, the benefit of the endovascular treatment is clearly greater than that of standard medical treatment in terms of favorable functional outcome. Conclusions: Body temperature is an independent predictor of clinical outcome in patients with acute basilar artery occlusion. It is necessary to control the patient body temperature within the appropriate range in clinical settings. Trial Registration: Chinese Clinical Trial Registry ChiCTR1800014759. Registered 03 February 2018. Retrospectively registered.

Phosphorus/Phosphide-Based Materials for Alkali Metal-Ion Batteries.

Phosphorus- and phosphide-based materials with remarkable physicochemical properties and low costs have attracted significant attention as the anodes of alkali metal (e.g., Li, Na, K, Mg, Ca)-ion batteries (AIBs). However, the low electrical conductivity and large volume expansion of these materials during electrochemical reactions inhibit their practical applications. To solve these problems, various promising solutions have been explored and utilized. In this review, the recent progress in AIBs using phosphorus- and phosphide-based materials is summarized. Thereafter, the in-depth working principles of diverse AIBs are discussed and predicted. Representative works with design concepts, construction approaches, engineering strategies, special functions, and electrochemical results are listed and discussed in detail. Finally, the existing challenges and issues are concluded and analyzed, and future perspectives and research directions are given. This review can provide new guidance for the future design and practical applications of phosphorus- and phosphide-based materials used in AIBs.

In Situ Constructed Ionic-Electronic Dual-Conducting Scaffold with Reinforced Interface for High-Performance Sodium Metal Anodes.

The formation of severe dendritic sodium (Na) microstructure reduces the reversibility of anode and further hinders its practical implementation. In this work, an ionic-electronic dual-conducting (IEDC) scaffold composed of Na3 P and carbon nanotubes is in situ developed by a scalable strategy with subsequent alloying reaction, for realizing dendrite-free Na deposition under high current density and large areal capacity. The in situ formed Na3 P with high sodiophilicity not only sets up a hierarchically efficient ionic conducting network, but also participates in the construction of reinforced solid electrolyte interphase, while carbon nanotubes can assemble an electronic conducting framework. As a result, the multifunctional IEDC scaffold contributes to smooth Na plating and exceptionally reversible Na stripping. High average Coulombic efficiency of 99.8% after prolonged 1200 cycles at 3 mA cm-2 and small overpotential of 20 mV over 250 h (equals to 530 cycles) at high rate of 5 mA cm-2 are obtained. The high availability of Na in IEDC scaffold enables the impressive performance of full cell with limited Na, using Na3 V2 (PO4 )3 (NVP) cathode at practical level. More importantly, the as-developed anode-free full cell with IEDC||NVP configuration delivers a high capacity retention with long lifetime, indicating its great potential for practical Na metal batteries.

Sodiophilically Graded Gold Coating on Carbon Skeletons for Highly Stable Sodium Metal Anodes.

Metallic sodium (Na) is an appealing anode material for high-energy Na batteries. However, Na metal suffers from low coulombic efficiencies and severe dendrite growth during plating/stripping cycles, causing short circuits. As an effective strategy to improve the deposition behavior of Na metal, a 3D carbon foam is developed that is sputter-coated with gold nanoparticles (Au/CF), forming a functional gradient through its thickness. The highly porous Au/CF host is proven to have gradually varying sodiophilicity, which in turn facilitates initially preferential Na deposition on the gold-rich, sodiophilic region in a "bottom-up growth" mode, leading to uniform plating over the entire Au/CF host. This finding contrasts with dendrite formation in the pristine CF host, as proven by in situ microscopy. The Na-predeposited Au/CF (Na@Au/CF) composite anode operates steadily for 1000 h at a low overpotential of ≈20 mV at 2 mA cm-2 in a symmetric cell. When the composite anode is coupled with a Na3 V2 (PO4 )2 F3 cathode, the full cell has a high capacity of 102.1 mAh g-1 after 500 cycles at 2 C. The sodiophilicity gradient design that is explored in this study offers new insight into developing porous Na metal hosts with highly stable plating/stripping performance for next-generation Na batteries.

Molybdenum Disulfide Based Nanomaterials for Rechargeable Batteries.

The rapid development of electrochemical energy storage systems requires new electrode materials with high performance. As a two-dimensional material, molybdenum disulfide (MoS2 ) has attracted increasing interest in energy storage applications due to its layered structure, tunable physical and chemical properties, and high capacity. In this review, the atomic structures and properties of different phases of MoS2 are first introduced. Then, typical synthetic methods for MoS2 and MoS2 -based composites are presented. Furthermore, the recent progress in the design of diverse MoS2 -based micro/nanostructures for rechargeable batteries, including lithium-ion, lithium-sulfur, sodium-ion, potassium-ion, and multivalent-ion batteries, is overviewed. Additionally, the roles of advanced in situ/operando techniques and theoretical calculations in elucidating fundamental insights into the structural and electrochemical processes taking place in these materials during battery operation are illustrated. Finally, a perspective is given on how the properties of MoS2 -based electrode materials are further improved and how they can find widespread application in the next-generation electrochemical energy-storage systems.

Nitrogen-doped graphene fiber webs for multi-battery energy storage.

Freestanding carbon-based electrodes with large surface areas and pore volumes are essential to fast ion transport and long-term energy storage. Many of the current porous carbon substrates are composed of particulates, making it difficult to form a self-supported structure. Herein, novel highly porous nitrogen-doped graphene fiber webs (N-GFWs) are prepared using a facile wet-spinning method. The wet chemical process facilitates simultaneous N-doping and surface wrinkling of graphene fibers in a one-pot process. The atomic structure and electrical conductivity of N-GFWs are tailored by tuning the degree of N-doping and thermal reduction for multi-battery charge storage in both lithium-oxygen batteries (LOBs) and lithium-sulfur batteries (LSBs). The N-GFW900 electrode presents an excellent electrocatalytic activity and the cathode with a high areal loading of 7.5 mg cm-2 delivers a remarkable areal capacity of 2 mA h cm-2 at 0.2 mA cm-2 for LOBs. The N-GFW700 interlayer with abundant oxygenated and nitrogen functional groups demonstrates effective entrapment of polysulfides in LSBs, delivering a much improved specific capacity after 200 cycles at 0.5C with a remarkable decay rate of 0.04%. The current approach paves the way for rational design of porous graphene-based electrodes, satisfying multifunctional requirements for high-energy storage applications.

Ultrafast-Charging and Long-Life Li-Ion Battery Anodes of TiO2-B and Anatase Dual-Phase Nanowires.

Ideal lithium-ion batteries (LIBs) should possess a high power density, be charged extremely fast (e.g., 100C), and have a long service life. To achieve them all, all battery components, including anodes, cathodes, and electrolytes should have excellent structural and functional characteristics. The present work reports ultrafast-charging and long-life LIB anodes made from TiO2-B/anatase dual-phase nanowires. The dual-phase nanowires are fabricated with anatase TiO2 nanoparticles through a facile and cost-effective hydrothermal process, which can be easily scaled up for mass production. The anodes exhibit remarkable electrochemical performance with reversible capacities of ∼225, 172, and 140 mAh g-1 at current rates of 1C, 10C, and 60C, respectively. They deliver exceptional capacity retention of not less than 126 and 93 mAh g-1 after 1000 cycles at 60C and 100C, respectively, potentially worthwhile for high-power applications. These values are among the best when the high-rate capabilities are compared with the literature data for similar TiO2-based anodes. The Ragone plot confirms both the exceptionally high energy and power densities of the devices prepared using the dual-phase nanowires. The electrochemical tests and operando Raman spectra present fast electrochemical kinetics for both Li+ and electron transports in the TiO2 dual-phase nanowires than in anatase nanoparticles due to the excellent Li+ diffusion coefficient and electronic conductivity of nanowires.

Ultrafine TiO2 Decorated Carbon Nanofibers as Multifunctional Interlayer for High-Performance Lithium-Sulfur Battery.

Although lithium-sulfur (Li-S) batteries deliver high specific energy densities, lots of intrinsic and fatal obstacles still restrict their practical application. Electrospun carbon nanofibers (CNFs) decorated with ultrafine TiO2 nanoparticles (CNF-T) were prepared and used as a multifunctional interlayer to suppress the volume expansion and shuttle effect of Li-S battery. With this strategy, the CNF network with abundant space and superior conductivity can accommodate and recycle the dissolved polysulfides for the bare sulfur cathode. Meanwhile, the ultrafine TiO2 nanoparticles on CNFs work as anchoring points to capture the polysulfides with the strong interaction, making the battery perform with remarkable and stable electrochemical properties. As a result, the Li-S battery with the CNF-T interlayer delivers an initial reversible capacity of 935 mA h g(-1) at 1 C with a capacity retention of 74.2% after 500 cycles. It is believed that this simple, low-cost and scalable method will definitely bring a novel perspective on the practical utilization of Li-S batteries.

Fabrication of Crack-Free Barium Titanate Thin Film with High Dielectric Constant Using Sub-Micrometric Scale Layer-by-Layer E-Jet Deposition.

Dense and crack-free barium titanate (BaTiO3, BTO) thin films with a thickness of less than 4 µm were prepared by using sub-micrometric scale, layer-by-layer electrohydrodynamic jet (E-jet) deposition of the suspension ink which is composed of BTO nanopowder and BTO sol. Impacts of the jet height and line-to-line pitch of the deposition on the micro-structure of BTO thin films were investigated. Results show that crack-free BTO thin films can be prepared with 4 mm jet height and 300 µm line-to-line pitch in this work. Dielectric constant of the prepared BTO thin film was recorded as high as 2940 at 1 kHz at room temperature. Meanwhile, low dissipation factor of the BTO thin film of about 8.6% at 1 kHz was also obtained. The layer-by-layer E-jet deposition technique developed in this work has been proved to be a cost-effective, flexible and easy to control approach for the preparation of high-quality solid thin film.