Wide-Temperature and High-Rate Operation of Lithium Metal Batteries Enabled by an Ionic Liquid Functionalized Quasi-Solid-State Electrolyte.

The development of high-energy-density solid-state lithium metal battery has been hindered by the unstable cycling of Ni-rich cathodes at high rate and limited wide-temperatures adoptability. In this study, an ionic liquid functionalized quasi-solid-state electrolyte (FQSE) is prepared to address these challenges. The FQSE features a semi-immobilized ionic liquid capable of anchoring solvent molecules through electrostatic interactions, which facilitates Li+ desolvation and reduces deleterious solvent-cathode reactions. The FQSE exhibits impressive electrochemical characteristics, including high ionic conductivity (1.9 mS cm-1 at 30 °C and 0.2 mS cm-1 at -30 °C) and a Li+ transfer number of 0.7. Consequently, Li/NCM811 cells incorporating FQSE demonstrate exceptional stability during high-rate cycling, enduring 700 cycles at 1 C. Notably, the Li/LFP cells with FQSE maintain high capacity across a wide temperature range, from -30 to 60 °C. This research provides a new way to promote the practical application of high-energy lithium metal batteries.

Recent Progress in Hot Spot Regulated Strategies for Catalysts Applied in Li-CO2 Batteries.

As a high energy density power system, lithium-carbon dioxide (Li-CO2 ) batteries play an important role in addressing the fossil fuel crisis issues and alleviating the greenhouse effect. However, the sluggish transformation kinetic of CO2 and the difficult decomposition of discharge products impede the achievement of large capacity, small overpotential, and long life span of the batteries, which require exploring efficient catalysts to resolve these problems. In this review, the main focus is on the hot spot regulation strategies of the catalysts, which include the modulation of the active sites, the designing of microstructure, and the construction of composition. The recent progress of promising catalysis with hot spot regulated strategies is systematically addressed. Critical challenges are also presented and perspectives to provide useful guidance for the rational design of highly efficient catalysts for practical advanced Li-CO2 batteries are proposed.

Strain Self-Adaptive Iron Selenides Toward Stable Na+-Ion Batteries with Impressive Initial Coulombic Efficiency.

High tap density electrodes play a vital role in developing rechargeable batteries with high volumetric capacities, however, developing advanced electrodes with satisfied capacity, excellent structural stability, and achieving the resulted batteries with a high initial Coulombic efficiency (ICE) and good rate capability with long lifespan simultaneously, are still an intractable challenge. Herein, an ultrahigh ICE of 94.1% and stable cycling of carbon-free iron selenides anode is enabled with a high tap density of 2.57 g cm-3 up to 4000 cycles at 5 A g-1 through strain-modulating by constructing a homologous heterostructure. Systematical characterization and theoretical calculation show that the self-adaptive homologous heterointerface alleviates the stress of the iron selenide anodes during cycling processes and subsequently improves the stability of the assembled batteries. Additionally, the well-formed homologous heterostructure also contributes to the rapid Na+ diffusion kinetic, increased charge transfer, and good reversibility of the transformation reactions, endowing the appealing rate capability of carbon-free iron selenides. The proposed design strategy provides new insight and inspiration to aid in the ongoing quest for advanced electrode materials with high tap densities and excellent stability.

Reductive Competition Effect-Derived Solid Electrolyte Interphase with Evenly Scattered Inorganics Enabling Ultrahigh Rate and Long-Life Span Sodium Metal Batteries.

Constructing an inorganic-rich and robust solid electrolyte interphase (SEI) is one of the crucial approaches to improving the electrochemical performance of sodium metal batteries (SMBs). However, the low conductivity and distribution of common inorganics in SEI disturb Na+ diffusion and induce nonuniform sodium deposition. Here, we construct a unique SEI with evenly scattered high-conductivity inorganics by introducing a self-sacrifice LiTFSI into the sodium salt-base carbonate electrolyte. The reductive competition effect between LiTFSI and FEC facilitates the formation of the SEI with evenly scattered inorganics. In which the high-conductive Li3N and inorganics provide fast ions transport domains and high-flux nucleation sites for Na+, thus conducive to rapid sodium deposition at a high rate. Therefore, the SEI derived from LiTFSI and FEC enables the Na∥Na3V2(PO4)3 cell to show 89.15% capacity retention (87.62 mA h g-1) at an ultrahigh rate of 60 C after 10,000 cycles, while the cell without LiTFSI delivers only 48.44% capacity retention even after 8000 cycles. Moreover, the Na∥Na3V2(PO4)3 pouch cell with the special SEI presents a stable capacity retention of 92.05% at 10 C after 2000 cycles. This unique SEI design elucidates a new strategy to propel SMBs to operate under extreme high-rate conditions.

Synergistic Engineering of Se Vacancies and Heterointerfaces in Zinc-Cobalt Selenide Anode for Highly Efficient Na-Ion Batteries.

The exploitation of effective strategies to accelerate the Na+ diffusion kinetics and improve the structural stability in the electrode is extremely important for the development of high efficientcy sodium-ion batteries. Herein, Se vacancies and heterostructure engineering are utilized to improve the Na+ -storage performance of transition metal selenides anode prepared through a facile two-in-one route. The experimental results coupled with theoretical calculations reveal that the successful construction of the Se vacancies and heterostructure interfaces can effectively lower the Na+ diffusion barrier, accelerate the charge transfer efficiency, improve Na+ adsorption ability, and provide an abundance of active sites. Consequently, the batteries based on the constructed ZnSe/CoSe2 -CN anode manifest a high initial Coulombic efficiency (97.7%), remarkable specific capacities (547.1 mAh g-1 at 0.5 A g-1 ), superb rate capability (362.1 mAh g-1 at 20 A g-1 ), as well as ultrastable long-term stability (1000 cycles) with a satisfied specific capacity (535.6 mAh g-1 ) at 1 A g-1 . This work facilitates an in-depth understanding of the synergistic effect of vacancies and heterojunctions in improving the Na+ reaction kinetics, providing an effective strategy to the rational design of key materials for high efficiency rechargeable batteries.

The role of ß-catenin in pulmonary artery endothelial-mesenchymal transformation in rats with chronic thromboembolic pulmonary hypertension.

ß-catenin and endothelial mesenchymal transformation play an important role in the formation of pulmonary hypertension. To explore the role of ß-catenin in chronic thromboembolic pulmonary hypertension (CTEPH), we first established a rat model of CTEPH by repeated autologous thromboembolization and then treated these rats with a ß-catenin specific inhibitor, XAV939, for two or four weeks. We further examined the expression of ß-catenin, α-SMA and CD31, mean pulmonary artery pressure (mPAP), and histopathology in the pulmonary artery, and analyzed their correlation. In the thrombus group without treatment of the inhibitor, the expression of ß-catenin and α-SMA in pulmonary artery was increased with time; mPAP, the thickness of pulmonary artery wall, and the area/total area of pulmonary artery (WA/TA) were also increased; however, the expression of CD31 was decreased. Interestingly, these symptoms could be improved by treatment with XAV939. In this study, in CTEPH rat model, the expression of ß-catenin signal affects pulmonary vascular remodeling and pulmonary artery pressure, and positively correlated with pulmonary arterial endothelial mesenchymal transformation (EMT), indicating that ß-catenin signal may play an important role in the occurrence and development of CTEPH. The inhibition of ß-catenin signal and the improvement of pulmonary arterial EMT may provide therapeutic ideas for CTEPH.

Amidation-Dominated Re-Assembly Strategy for Single-Atom Design/Nano-Engineering: Constructing Ni/S/C Nanotubes with Fast and Stable K-Storage.

An amidation-dominated re-assembly strategy is developed to prepare uniform single atom Ni/S/C nanotubes. In this re-assembly process, a single-atom design and nano-structured engineering are realized simultaneously. Both the NiO5 single-atom active centers and nanotube framework endow the Ni/S/C ternary composite with accelerated reaction kinetics for potassium-ion storage. Theoretical calculations and electrochemical studies prove that the atomically dispersed Ni could enhance the convention kinetics and decrease the decomposition energy barrier of the chemically-absorbed small-molecule sulfur in Ni/S/C nanotubes, thus lowering the electrode reaction overpotential and resistance remarkably. The mechanically stable nanotube framework could well accommodate the volume variation during potassiation/depotassiation process. As a result, a high K-storage capacity of 608 mAh g-1 at 100 mA g-1 and stable cycling capacity of 330.6 mAh g-1 at 1000 mA g-1 after 500 cycles are achieved.

In Situ Tracking of Organic Reactions at the Vapor/Liquid Interfaces of Ionic Liquids.

The molecular structures of ionic liquids at interfaces play a crucial role in determining their chemical activities in applications. In situ X-ray photoelectron spectroscopy (XPS) was used to track the evolution of X-ray irradiation-induced chemical reactions in a series of ionic liquids ([Cn mim][AuCl4 ]; n=4, 6, 8, 10) on the Si (111) single-crystal surface. Analyses of microstructure and chemical bonding based on the XPS results indicated that reactions occurred at the vapor/liquid interfaces of the ionic liquids. The time-resolved XPS spectra revealed that with increasing irradiation time, the intensity of the peak corresponding to trivalent Au anion decreased for the four ionic liquids as Au was continually reduced to a lower chemical state and finally converted to gold nanoparticles. The rate and conversion of the reaction were associated with the length of the alkyl chain of the ionic liquids cation. Molecular dynamics simulations further revealed that the alkyl chain of the cation in the ionic liquids was oriented towards the vacuum environment at the vapor/liquid interface. Our results provide a real-time atomic-scale experimental evidence of organic reactions at the vapor/liquid interfaces of ionic liquids. The findings are important for understanding the roles of ionic liquids in catalysis, separation, electrochemistry, functional materials, and so on.

Boosting PEC performance of Si photoelectrodes by coupling bifunctional CuCo hybrid oxide cocatalysts.

Silicon (Si) is an attractive candidate for photoelectrochemical (PEC) water splitting because of its small band gap, fast carrier mobility and abundant reserves. However, the PEC performance has been severely limited by the sluggish kinetics of oxygen/hydrogen evolution reaction at the Si photoelectrode/electrolyte interface and poor stability in the aqueous environment. Herein, the bifunctional CuCo hybrid oxides (CuCo-HO) cocatalysts have been integrated with ultrathin TiO2 decorated n-type and p-type Si nanowires (NWs) to simultaneously improve the photoactivity and stability of Si photoelectrodes. The thickness of TiO2 layer, the concentration of CuCo-precursor and the hydrothermal reaction time have been investigated to optimize the PEC performance. The enhancement mechanism is studied and mainly ascribed to the increased light harvesting, small charge transfer resistance and high carrier density of Si NWs/TiO2/CuCo-HO photoelectrodes.

Probing the spontaneous reduction mechanism of platinum ions confined in the nanospace by X-ray absorption fine structure spectroscopy.

The reduction mechanism of Pt(4+) ions confined in the channel of multi-walled carbon nanotubes was mainly investigated using X-ray absorption fine structure (XAFS) spectroscopy, with the aid of TEM, Raman, XRD and ICP-AES studies. The XAFS spectra revealed the spontaneous formation of Pt nanoparticles when H2PtCl6 was confined in multi-walled carbon nanotubes (MWCNTs). The Pt L3-edge X-ray absorption near edge structure (XANES) coupled with the C K-edge NEXAFS results indicated that the reduction of Pt(4+) from tetravalent to zerovalent was attributed to the electron transfer from MWCNTs. The Fourier transform R-space of the Pt L3-edge XAFS data displayed that the nanoconfinement effect of MWCNTs promoted the formation of Pt nanoparticles. Moreover, the Pt-Pt bond length in confined Pt nanoparticles became shorter than that of Pt in the bulk state. Furthermore, by varying the inner diameter of MWCNTs from 15 nm to 10 nm and 5 nm, the Pt-Pt bond length of nanoconfined Pt nanoparticles decreased gradually. The results clearly revealed that MWCNTs acting as enriched electron donors can continuously reduce the confined Pt ions to Pt nanoparticles, thereby showing a great potential for the design of a new type of confined nanocatalysts.

Ionic liquid clusters: structure, formation mechanism, and effect on the behavior of ionic liquids.

The microstructure of ionic liquids (ILs) has attracted much attention due to their relevance in physiochemical properties and behavior of ILs. The existence of clusters (or microheterogeneous structure) is one of the main features for many ILs, which provides fundamental information for understanding the performance of ILs in their applications. This perspective concentrates on the recent progresses in IL clusters research. Firstly, we give a brief introduction on the structure of clusters in neat ILs and IL solutions. Secondly, the possible formation mechanism of the IL clusters is described. Then, the effects of the clusters on the physicochemical properties, interfacial properties, confined geometry and assembly processes of ILs are discussed. Finally, we address the associated challenges and prospects on the future study of IL clusters.

Electrolytes Design for Extending the Temperature Adaptability of Lithium-Ion Batteries: from Fundamentals to Strategies.

With the continuously growing demand for wide-range applications, lithium-ion batteries (LIBs) are increasingly required to work under conditions that deviate from room temperature (RT). However, commercial electrolytes exhibit low thermal stability at high temperatures (HT) and poor dynamic properties at low temperatures (LT), hindering the operation of LIBs under extreme conditions. The bottleneck restricting the practical applications of LIBs has promoted researchers to pay more attention to developing a series of innovative electrolytes. This review primarily covers the design of electrolytes for LIBs from a temperature adaptability perspective. First, the fundamentals of electrolytes concerning temperature, including donor number (DN), dielectric constant, viscosity, conductivity, ionic transport, and theoretical calculations are elaborated. Second, prototypical examples, such as lithium salts, solvent structures, additives, and interfacial layers in both liquid and solid electrolytes, are presented to explain how these factors can affect the electrochemical behavior of LIBs at high or low temperatures. Meanwhile, the principles and limitations of electrolyte design are discussed under the corresponding temperature conditions. Finally, a summary and outlook regarding electrolytes design to extend the temperature adaptability of LIBs are proposed.

Bond-Engineered MoSe2 Nanosheets with Expanded Layers and an Enriched 1T Phase for Highly Efficient Na+ Storage.

MoSe2 has attracted significant interest for Na+ storage due to its large interlayer distance, favorable band gap structure, and satisfying theoretical specific capacity. Nevertheless, the poor conductivity and large volume stress/strain always lead to poor cycle stability and limited rate capability. Herein, the P-Se bond and phase engineering strategies are proposed to enhance the stability of MoSe2 with the assistance of carbon compositing. Systematical characterizations confirm that the presence of a strong P-Se bond can ensure the good structural stability and enlarge the layer distance of the MoSe2 anode. 1T phase-enriched composition endows excellent conductivity and thus fast Na+ transport kinetics. Additionally, the combination of carbon contributes to the improvement of electron conductivity, further enhancing the reversible Na+ storage and cyclic stability. Consequently, an ultrastable reversible specific capacity of 347.8 mAh g-1 with a high retention ratio of 99.1% can be maintained after 1000 cycles at 1 A g-1, which is superior to the previous reports of MoSe2 nanosheets. The presented strategy is ingenious, offering an effective guidance to designing advanced electrodes to be applied in rechargeable batteries with a long lifespan.

Insight into Sulfur-Containing Zwitter-Molecule Boosting Zn Anode: from Electrolytes to Electrodes.

Numerous organic electrolytes additives have been reported to improve Zn anode performance in aqueous Zn metal batteries (AZMBs). However, the modification mechanism needs to be further revealed in consideration of different environments for electrolytes and electrodes during the charge-discharge process. Herein, sulfur-containing zwitter-molecule (methionine, Met) is used as an additive for ZnSO4 electrolytes. In electrolytes, Met reduces the H2O coordination number and facilitates the desolvation process by virtue of functional groups (─COOH, ─NH2, C─S─C), accelerating Zn2+ transference kinetics and decreasing the amount of active water. On electrodes, Met prefers to adsorb on Zn (002) plane and further transforms into a zincophilic protective layer containing C─SOx─C through an in situ electrochemical oxidization, suppressing H2 evolution/corrosion reactions and guiding dendrite-free Zn deposition. By using Met-containing ZnSO4 electrolytes, the Zn//Zn cells show superior cycling performance under 30 mA cm-2/30 mA h cm-2. Moreover, the full cells Zn//NH4V4O10 full cells using the modified electrolytes exhibit good performance at temperatures from -8 to 60 °C. Notably, a high energy density of 105.30 W h kg-1 can be delivered using a low N/P ratio of 1.2, showing a promising prospect of Met electrolytes additives for practical use.

Recent advances in electrospinning nanofiber materials for aqueous zinc ion batteries.

Aqueous zinc ion batteries (AZIBs) are regarded as one of the most promising large-scale energy storage systems because of their considerable energy density and intrinsic safety. Nonetheless, the severe dendrite growth of the Zn anode, the serious degradation of the cathode, and the boundedness of separators restrict the application of AZIBs. Fortunately, electrospinning nanofibers demonstrate huge potential and bright prospects in constructing AZIBs with excellent electrochemical performance due to their controllable nanostructure, high conductivity, and large specific surface area (SSA). In this review, we first briefly introduce the principles and processing of the electrospinning technique and the structure design of electrospun fibers in AZIBs. Then, we summarize the recent advances of electrospinning nanofibers in AZIBs, including the cathodes, anodes, and separators, highlighting the nanofibers' working mechanism and the correlations between electrode structure and performance. Finally, based on insightful understanding, the prospects of electrospun fibers for high-performance AZIBs are also presented.

Durable and Adjustable Interfacial Engineering of Polymeric Electrolytes for Both Stable Ni-Rich Cathodes and High-Energy Metal Anodes.

Achieving stable cycling of high-voltage solid-state lithium metal batteries is crucial for next-generation rechargeable batteries with high energy density and high safety. However, the complicated interface problems in both cathode/anode electrodes preclude their practical applications hitherto. Herein, to simultaneously solve such interfacial limitations and obtain sufficient Li+ conductivity in the electrolyte, an ultrathin and adjustable interface is developed at the cathode side through a convenient surface in situ polymerization (SIP), achieving a durable high-voltage tolerance and Li-dendrite inhibition. The integrated interfacial engineering fabricates a homogeneous solid electrolyte with optimized interfacial interactions that contributes to tame the interfacial compatibility between LiNix Coy Mnz O2 and polymeric electrolyte accompanied by anticorrosion of aluminum current collector. Further, the SIP enables a uniform adjustment of solid electrolyte composition by dissolving additives such as Na+ and K+ salts, which presents prominent cyclability in symmetric Li cells (>300 cycles at 5 mA cm-2 ). The assembled LiNi0.8 Co0.1 Mn0.1 O2 (4.3 V)||Li batteries show excellent cycle life with high Coulombic efficiencies (>99%). This SIP strategy is also investigated and verified in sodium metal batteries. It opens a new frontier for solid electrolytes toward high-voltage and high-energy metal battery technologies.

Recent Advances in Electrolytes for "Beyond Aqueous" Zinc-Ion Batteries.

With the growing demands for large-scale energy storage, Zn-ion batteries (ZIBs) with distinct advantages, including resource abundance, low-cost, high-safety, and acceptable energy density, are considered as potential substitutes for Li-ion batteries. Although numerous efforts are devoted to design and develop high performance cathodes and aqueous electrolytes for ZIBs, many challenges, such as hydrogen evolution reaction, water evaporation, and liquid leakage, have greatly hindered the development of aqueous ZIBs. Developing "beyond aqueous" electrolytes can be able to avoid these issues due to the absence of water, which are beneficial for the achieving of highly efficient ZIBs. In this review, the recent development of the "beyond aqueous" electrolytes, including conventional organic electrolytes, ionic liquid, all-solid-state, quasi-solid-state electrolytes, and deep eutectic electrolytes are presented. The critical issues and the corresponding strategies of the designing of "beyond aqueous" electrolytes for ZIBs are also summarized.

Semi-Immobilized Ionic Liquid Regulator with Fast Kinetics toward Highly Stable Zinc Anode under -35 to 60 °C.

Aqueous zinc ion batteries (ZIBs) have been extensively investigated as a next-generation energy storage system due to their high safety and low cost. However, the critical issues of irregular dendrite growth and intricate side reactions severely restrict the further industrialization of ZIBs. Here, a strategy to fabricate a semi-immobilized ionic liquid interface layer is proposed to protect the Zn anode over a wide temperature range from -35 to 60 °C. The immobilized SiO2 @cation can form high conjugate racks that can regulate the Zn2+ concentration gradient and self-polarizing electric field to guarantee uniform nucleation and planar deposition; the free anions of the ILs can weaken the hydrogen bonds of the water to promote rapid Zn2+ desolvation and accelerate ion-transport kinetics simultaneously. Because of these unique advantages, the cycling performance of the symmetric Zn batteries is greatly enhanced, evidenced by a cycling life of 1800 h at 20 mA cm-2 , and a cycle lifespan of 2000 h under a wide temperature window from -35 to 60 °C. The efficiency of this semi-immobilizing strategy is well demonstrated in various full cells including pouch cells, showing high performance at large current (20 A g-1 ) and wide temperatures with extra-long cycles up to 80 000 cycles.

Symptomatic Complete Discoid Medial Meniscus Completely Coalesced with the Anterior Cruciate Ligament: A Case Report and Literature Review.

BACKGROUND: Complete discoid medial meniscus is an extremely rare abnormality of the knee joint whose meniscus has a discoid shape rather than a normal semilunar one. Several medial meniscus anomalies including anomalous insertion have been reported in the literature. This report presents a rare case of symptomatic complete discoid medial meniscus whose anterolateral (apical) portion was completely coalesced with the ACL. MRI, radiographic, and arthroscopic findings in the medial compartment are to be submitted. CASE PRESENTATION: A 29-year-old male presented with intermittent pain and swelling of the right knee for 2 years. Based on radiographic, MRI, and physical examination findings, he was diagnosed with discoid medial meniscus tears. Arthroscopic saucerization was performed for the torn discoid medial meniscus of the right knee. Arthroscopic examination revealed a complete discoid medial meniscus and the anterolateral (apical) portion of which was completely coalesced with the ACL. Careful Probing of the meniscal surface revealed there was a longitudinal tear extending from the tibial spine to the midportion of the meniscus. Arthroscopic saucerization of the discoid meniscus was performed after closely cutting the meniscus around the ACL. The patient reported no symptoms, and he had returned to his daily and sports activities, including football, basketball, and jogging, at the 12-month follow-up. CONCLUSION: Complete discoid medial meniscus is an extremely rare abnormality, and this case presents the third complete discoid medial meniscus whose anterolateral (apical) portion was completely coalesced with the ACL. The current case we present strongly supports the hypothesis that ACL and meniscus were differentiated from the same mesenchyme.

Simultaneously Stabilizing Both Electrodes and Electrolytes by a Self-Separating Organometallics Interface for High-Performance Zinc-Ion Batteries at Wide Temperatures.

Rechargeable aqueous zinc-ion batteries are of great potential as one of the next-generation energy-storage devices due to their low cost and high safety. However, the development of long-term stable electrodes and electrolytes still suffers from great challenges. Herein, a self-separation strategy is developed for an interface layer design to optimize both electrodes and electrolytes simultaneously. Specifically, the coating with an organometallics (sodium tricyanomethanide) evolves into an electrically responsive shield layer composed of nitrogen, carbon-enriched polymer network, and sodium ions, which not only modulates the zinc-ion migration pathways to inhibit interface side reactions but also adsorbs onto Zn perturbations to induce planar zinc deposition. Additionally, the separated ions from the coating can diffuse to the electrolyte to affect the Zn2+ solvation structure and maintain the cathode structural stability by forming a stable cathode-electrolyte interface and sodium ions' equilibrium, confirmed by in situ spectroscopy and electrochemical analysis. Due to these unique advantages, the symmetric zinc batteries exhibit an extralong cycling lifespan of 3000 h and rate performance at 20 mA cm-2 at wide temperatures. The efficiency of the self-separation strategy is further demonstrated in practical full batteries with an ultralong lifespan over 10 000 cycles from -35 to 60 °C.