A Universal Self-Propagating Synthesis of Aluminum-Based Oxyhalide Solid-State Electrolytes.

Inorganic solid-state electrolytes (SSEs) play a vital role in high-energy all-solid-state batteries (ASSBs). However, the current method of SSE preparation usually involves high-energy mechanical ball milling and/or a high-temperature annealing process, which is not suitable for practical application. Here, a facile strategy is developed to realize the scalable synthesis of cost-effective aluminum-based oxyhalide SSEs, which involves a self-propagating method by the exothermic reaction of the raw materials. This strategy enables the synthesis of various aluminum-based oxyhalide SSEs with tunable components and high ionic conductivities (over 10-3 S cm-1 at 25 °C) for different cations (Li+, Na+, Ag+). It is elucidated that the amorphous matrix, which mainly consists of various oxidized chloroaluminate species that provide numerous sites for smooth ion migration, is actually the key factor for the achieved high conductivities. Benefit from their easy synthesis, low cost, and low weight, the aluminum-based oxyhalide SSEs synthesized by our approach could further promote practical application of high-energy-density ASSBs.

Structural regulation of halide superionic conductors for all-solid-state lithium batteries.

Metal halide solid-state electrolytes have gained widespread attention due to their high ionic conductivities, wide electrochemical stability windows, and good compatibility with oxide cathode materials. The exploration of highly ionic conductive halide electrolytes is actively ongoing. Thus, understanding the relationship between composition and crystal structure can be a critical guide for designing better halide electrolytes, which still remains obscure for reliable prediction. Here we show that the cationic polarization factor, which describes the geometric and ionic conditions, is effective in predicting the stacking structure of halide electrolytes formation. By supplementing this principle with rational design and preparation of more than 10 lithium halide electrolytes with high conductivity over 10-3 S cm-1 at 25 °C, we establish that there should be a variety of promising halide electrolytes that have yet to be discovered and developed. This methodology may enable the systematic screening of various potential halide electrolytes and demonstrate an approach to the design of halide electrolytes with superionic conductivity beyond the structure and stability predictions.

The Universal Super Cation-Conductivity in Multiple-cation Mixed Chloride Solid-State Electrolytes.

As exciting candidates for next-generation energy storage, all-solid-state lithium batteries (ASSLBs) are highly dependent on advanced solid-state electrolytes (SSEs). Here, using cost-effective LaCl3 and CeCl3 lattice (UCl3 -type structure) as the host and further combined with a multiple-cation mixed strategy, we report a series of UCl3 -type SSEs with high room-temperature ionic conductivities over 10-3  S cm-1 and good compatibility with high-voltage oxide cathodes. The intrinsic large-size hexagonal one-dimensional channels and highly disordered amorphous phase induced by multi-metal cation species are believed to trigger fast multiple ionic conductions of Li+ , Na+ , K+ , Cu+ , and Ag+ . The UCl3 -type SSEs enable a stable prototype ASSLB capable of over 3000 cycles and high reversibility at -30 °C. Further exploration of the brand-new multiple-cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density.

Research Trends and Foci in Osteoarthritis Pain from 2012 to 2022: Bibliometric and Visualization Study.

Background: Osteoarthritis (OA) is a painful and complex joint disease. The unique mechanisms and potential interventions of OA-induced pain have attracted researchers' attention in recent years. Bibliometric and visualization analysis is a comprehensive scientific method that integrates mathematical and statistical approaches to explore research priorities in a specific field. However, there are few studies on OA pain using bibliometric analysis. Purpose: This study aimed to explore research trends and hotspots in OA pain research field, offer practical guidance to researchers looking for top-notch scholars/institutions/countries, and provide suggestions for journal submissions by analyzing the existing literature. Methods: Raw data were extracted from Web of Science Core Collection. Microsoft Excel, the R package "bibliometrix", VOSviewer and CiteSpace software were used to analyze data and visualize relevant results. Results: A total of 2493 articles were included for further bibliometric and visualization analysis. During the investigated period, 2021 with 343 publications was the most productive year. Fillingim, Roger B. and Bennell, Kim L. with 32 articles were the most productive authors. Most publications were from the USA (797 articles, 20,727 citations). Rehabilitation and treatment of OA pain were the hotspots in OA pain research area. The top-contributing journal was Osteoarthritis and Cartilage. Boston University (91 articles; 4050 citations) was the most active institution. Conclusion: The total publications of OA pain generally increasing over the time in the last decade, and the escalating rate remained a high level. This is the first comprehensive bibliometric study in OA pain research field, and it will offer practical guidance to researchers in this field.

Association between serum soluble α-klotho and bone mineral density (BMD) in middle-aged and older adults in the United States: a population-based cross-sectional study.

BACKGROUND: Osteoporosis is a degenerative disease defined by low bone mineral density, has a high prevalence, and causes fractures at multiple sites throughout the body, greatly affecting the quality of patients. α-Klotho is an endocrine factor involved in the regulation of various metabolic processes in humans, and its role in bone metabolism has attracted widespread attention. The relationship between α-klotho and bone mineral density has not been uniformly recognized, and no large-scale correlation analysis has been conducted in the middle-aged and elderly population. OBJECTIVE: To determine the relationship between α-klotho and bone mineral density in middle-aged and elderly people. METHODS: Population data of 3120 individuals aged 40-79 years were obtained from the NHANES database for the period 2011-2016. Regression analysis was performed using a general linear model with serum α-klotho as the independent variable and total bone mineral density, thoracic bone mineral density, lumbar bone mineral density, pelvic bone mineral density, and trunk bone mineral density as the dependent variables, respectively. The generalized additive model was also used for smoothing curve fitting and threshold effect analysis. RESULTS: Serum α-klotho was positively correlated with total bone mineral density at lg (Klotho) < 2.97 and with thoracic bone mineral density at lg (Klotho) > 2.69 (ß = 0.05, p = 0.0006), and negatively correlated (ß = -0.27, p = 0.0341) with lumbar bone mineral density at lg (Klotho) < 2.69. It also positively correlated with trunk bone mineral density (ß = 0.027, p = 0.03657) and had no segmental effect but did not correlate with pelvic bone mineral density. The positive association of serum α-klotho with those aged 40-49 years, female, non-Hispanic White, and without hypertension was clearer. In the population with diabetes, a significantly positive association between total (ß = 0.15, p = 0.01), thoracic (ß = 0.23, p = 0.0404), and lumbar (ß = 0.22, p = 0.0424) bone mineral density and α-klotho was observed. CONCLUSIONS: α-Klotho has different relationships with total, thoracic, lumbar, and trunk bone mineral density. Among them, the positive correlation between α-klotho and trunk bone mineral density is more valuable for predicting osteoporosis. The significant effect of α-klotho on bone mineral density in diabetes patients suggests its potential as a predictive marker of diabetes progression.

Regulating the Lithium Ions' Local Coordination Environment through Designing a COF with Single Atomic Co Site to Achieve Dendrite-Free Lithium-Metal Batteries.

The detrimental growth of lithium dendrites and unstable solid electrolyte interphase (SEI) inhibit the practical application of lithium-metal batteries. Herein, atomically dispersed cobalt coordinate conjugated bipyridine-rich covalent organic framework (sp2 c-COF) is explored as an artificial SEI on the surface of the Li-metal anode to resolve these issues. The single Co atoms confined in the structure of COF enhance the number of active sites and promote electron transfer to the COF. The synergistic effects of the Co─N coordination and strong electron-withdrawing cyano-group can adsorb the electron from the donor (Co) at a maximum and create an electron-rich environment, hence further regulating the Li+ local coordination environment and achieving uniform Li-nucleation behavior. Furthermore, in situ technology and density functional theory calculations reveal the mechanism of the sp2 c-COF-Co inducing Li uniform deposition and promoting Li+ rapid migration. Based on these advantages, the sp2 c-COF-Co modified Li anode exhibits a low Li-nucleation barrier of 8 mV, and excellent cycling stability of 6000 h.

Hopping Rate and Migration Entropy as the Origin of Superionic Conduction within Solid-State Electrolytes.

Inorganic solid-state electrolytes (SSEs) have gained significant attention for their potential use in high-energy solid-state batteries. However, there is a lack of understanding of the underlying mechanisms of fast ion conduction in SSEs. Here, we clarify the critical parameters that influence ion conductivity in SSEs through a combined analysis approach that examines several representative SSEs (Li3YCl6, Li3HoCl6, and Li6PS5Cl), which are further verified in the xLiCl-InCl3 system. The scaling analysis on conductivity spectra allowed the decoupled influences of mobile carrier concentration and hopping rate on ionic conductivity. Although the carrier concentration varied with temperature, the change alone cannot lead to the several orders of magnitude difference in conductivity. Instead, the hopping rate and the ionic conductivity present the same trend with the temperature change. Migration entropy, which arises from lattice vibrations of the jumping atoms from the initial sites to the saddle sites, is also proven to play a significant role in fast Li+ migration. The findings suggest that the multiple dependent variables such as the Li+ hopping frequency and migration energy are also responsible for the ionic conduction behavior within SSEs.

Ionic Conductive and Highly-Stable Interface for Alkali Metal Anodes.

Alkali metals are regarded as the most promising candidates for advanced anode for the next-generation batteries due to their high specific capacity, low electrochemical potential, and lightweight. However, critical problems of the alkali metal anodes, especially dendrite formation and interface stabilization, remain challenging to overcome. The solid electrolyte interphase (SEI) is a key factor affecting Li and Na deposition behavior and electrochemical performances. Herein, a facile and universal approach is successfully developed to fabricate ionic conductive interfaces for Li and Na metal anodes by modified atomic layer deposition (ALD). In this process, the Li metal (or Na metal) plays the role of Li (or Na) source without any additional Li (or Na) precursor during ALD. Moreover, the key questions about the influence of ALD deposition temperature on the compositions and structure of the coatings are addressed. The optimized ionic conductive coatings have significantly improved the electrochemical performances. In addition, the electrochemical phase-field model is performed to prove that the ionic conductive coating is very effective in promoting uniform electrodeposition. This approach is universal and can be potentially applied to other different metal anodes. At the same time, it can be extended to other types of coatings or other deposition techniques.

Transition of the Reaction from Three-Phase to Two-Phase by Using a Hybrid Conductor for High-Energy-Density High-Rate Solid-State Li-O2 Batteries.

Solid-state Li-O2 batteries possess the ability to deliver high energy density with enhanced safety. However, designing a highly functional solid-state air electrode is the main bottleneck for its further development. Herein, we adopt a hybrid electronic and ionic conductor to build solid-state air electrode that makes the transition of Li-O2 battery electrochemical mechanism from a three-phase process to a two-phase process. The solid-state Li-O2 battery with this hybrid conductor solid-state air electrode shows decreased interfacial resistance and enhanced reaction kinetics. The Coulombic efficiency of Li-O2 battery is also significantly improved, benefiting from the good contact between discharge products and electrode materials. In situ environmental transmission electron microscopy under oxygen was used to illustrate the reversible deposition and decomposition of discharge products on the surface of this hybrid conductor, visually verifying the two-phase reaction.

Interface Inversion: A Promising Strategy to Configure Ultrafine Nanoparticles over Graphene for Fast Sodium Storage.

Due to the merits of high activity and rapid reaction kinetics, ultrafine nanoparticles loaded on conductive scaffolds are of great potential in energy-related fields. Usually, the nucleation and uniform growth of these active nanoparticles in high density on scaffolds is governed by the local ion concentration gradient and nucleation sites at the interfaces. On account of this, a novel interface-inverting strategy is developed to modulate the diffusion of metal ions toward the nucleation sites, leading to the tuned growth of ultrafine nanoparticles anchored on graphene. Typically, the Ni(OH)2 deposited on graphene initially enables the interface inverting from oil-water-solid consisting of liquid paraffin (LP), water, and GO to water-oil-solid, finally resulting in LP-enveloped Ni(OH)2 /GO structure. In response, the inert-infiltrated LP layer inhibits the solubility and diffusion of nickel ions, which functions to modulate the growth and aggregation of adjacent nanoparticles. As a demonstration, the phosphorized Ni2 P@C/G as anode in sodium-ion capacitor can deliver a high energy density of 54 Wh kg-1 at a high power density of 23 kW kg-1 yet with a remarkable rate performance due to the surface-enhanced energy storage and fast Na+ transport enabled by the tuned surface/interface.

Ultrafast Construction of Oxygen-Containing Scaffold over Graphite for Trapping Ni2+ into Single Atom Catalysts.

Ultrafast construction of oxygen-containing scaffold over graphite for trapping Ni2+ into single atom catalysts (SACs) was developed and presented by a one-step electrochemical activation technique. The present method for Ni SACs starts with graphite foil and is capable of achieving ultrafast preparation (1.5 min) and mass production. The defective oxygen featuring the strong electronegativity enables primarily attracting Ni2+ ions and stabilizing Ni atoms via Ni-O6 coordination instead of conventional metal-C or metal-N. In addition, the oxygen defects for trapping are tunable through altering the applied voltage or electrolyte, further altering the loading of Ni atoms, indicative of enhanced oxygen evolution activity. This simple and ultrafast electrochemical synthesis is promising for the mass and controllable production of oxygen-coordinated Ni SACs, which exhibit good performance for oxygen evolution reaction.

Highly Stable Lithium Metal Anode Interface via Molecular Layer Deposition Zircone Coatings for Long Life Next-Generation Battery Systems.

Herein, molecular layer deposition is used to form a nanoscale "zircone" protective layer on Li metal to achieve stable and long life Li metal anodes. The zircone-coated Li metal shows enhanced air stability, electrochemical performance and high rate capability in symmetrical cell testing. Moreover, as a proof of concept, the protected Li anode is used in a next-generation Li-O2 battery system and is shown to extend the lifetime by over 10-fold compared to the batteries with untreated Li metal. Furthermore, in-situ synchrotron X-ray absorption spectroscopy is used for the first time to study an artificial SEI on Li metal, revealing the electrochemical stability and lithiation of the zircone film. This work exemplifies significant progress towards the development and understanding of MLD thin films for high performance next-generation batteries.

Electrochemically Driven Coordination Tuning of FeOOH Integrated on Carbon Fiber Paper for Enhanced Oxygen Evolution.

Coordination tuning of catalysts is a highly effective strategy for activating and improving the intrinsic activity. Herein, a Co-engineered FeOOH catalyst integrated on carbon fiber paper (Co-FeOOH/CFP) is reported, which realized a great improvement of the oxygen evolution activity by tuning the coordination geometry of the Fe species with an electrochemically driven method. Experiments and theoretical calculation demonstrate that the FeO bonds of FeOOH are partially broken, which is rooted in the Co incorporation, thus resulting in unsaturated FeO6 ligand structures and a relatively narrow bandgap. Consequently, the reorganized Fe sites on the surface show an enhanced capability for adsorbing OH- species and the Co-FeOOH exhibits an improved conductivity. As expected, the Co-FeOOH/CFP hybrids exhibit an extremely low overpotential of ≈250 mV at 10 mA cm-2 and a small Tafel slope, which far outperforms that of electrochemically sluggish FeOOH. The present work emphasizes the importance of local Fe coordination in catalysis and provides an in-depth insight into the mechanism of the enhanced catalytic activity.

Restructuring of Cu2O to Cu2O@Cu-Metal-Organic Frameworks for Selective Electrochemical Reduction of CO2.

Electrochemical reduction of carbon dioxide to hydrocarbons, driven by renewable power sources, is a fascinating and clean way to remedy greenhouse gas emission as a result of overdependence on fossil fuels and produce value-added fine chemicals. The Cu-based catalysts feature unique superiorities; nevertheless, achieving high hydrocarbon selectivity is still inhibited and remains a great challenge. In this study, we report on a tailor-made multifunction-coupled Cu-metal-organic framework (Cu-MOF) electrocatalyst by time-resolved controllable restructuration from Cu2O to Cu2O@Cu-MOF. The restructured electrocatalyst features a time-responsive behavior and is equipped with high specific surface area for strong adsorption capacity of CO2 and abundant active sites for high electrocatalysis activity based on the as-produced MOF on the surface of Cu2O, as well as the accelerated charge transfer derived from the Cu2O core in comparison with the Cu-MOF. These intriguing characteristics finally lead to a prominent performance towards hydrocarbons, with a high hydrocarbon Faradaic efficiency (FE) of 79.4%, particularly, the CH4 FE as high as 63.2% (at -1.71 V). This work presents a novel and efficient strategy to configure MOF-based materials in energy and catalysis fields, with a focus on big surface area, high adsorption ability, and much more exposed active sites.

Phosphate Species up to 70% Mass Ratio for Enhanced Pseudocapacitive Properties.

The emerging phosphate species on the surface or near-surface of electrode materials are versatile and have an intriguing ability for dramatically enhanced electrochemical performance. Unfortunately, the distribution/dispersion of phosphate species still keeps at levels on the exterior not within the interior surface of materials, and the micro-/nanoscale tuning is commonly rarely concerned and its function remains poorly understood. Herein, for the first time, well-dispersed phosphate species up to 70% mass ratio implanted within Ni-doped CoP nanowire matrix are presented via an efficient low-temperature phosphorization strategy. The resultant nanohybrids possess kinetics-favorable open frameworks with abundant mesopores and a high degree covalency in the chemical bonds, thus leading to rapid mass transport/charge transfer and enhanced redox reaction kinetics. Remarkably, the phosphate species feature superwettability toward water and strong affinity for OH- in the electrolyte, evidenced by the shortened distance and reduced adsorption energy between the OH- and the nuclear Co atoms on the nanohybrids as revealed by density functional theory calculations. As such, the nanohybrids exhibit an ultrahigh specific capacity of 250 mAh g-1 even at 50 A g-1 . This work presents a deeper understanding of the dispersion and role of phosphate species for supercapacitors and other energy-related storage/conversion devices.

Ultrahigh-Capacity and Long-Life Lithium-Metal Batteries Enabled by Engineering Carbon Nanofiber-Stabilized Graphene Aerogel Film Host.

A safe, high-capacity, and long-life Li metal anode is highly desired due to recent developments in high-energy-density Li-metal batteries. However, there are still rigorous challenges associated with the undesirable formation of Li dendrites, lack of suitable host materials, and unstable chemical interfaces. Herein, a carbon nanofiber-stabilized graphene aerogel film (G-CNF film), inspired by constructional engineering, is constructed. As the host material for Li deposition, the G-CNF film features a large surface area, porous structure, and a robust skeleton that can render low local current density. This allows for dendrite-free Li deposition and mitigation of problems associated with large volume change. Importantly, the G-CNF film can keep high Li plating/stripping efficiency at nearly 99% for over 700 h with an areal capacity of 10 mA h cm-2 (the specific capacity up to 2588 mA h g-1 based on the total mass of carbon host and Li metal). The symmetric cells can stably run for more than 1000 h with low voltage hysteresis. The full cell with the LiFePO4 cathode also delivers enhanced capacity and lowered overpotential. As two-in-one host materials for both cathodes and anodes in Li-O2 batteries, the battery exhibits a capacity of 1.2 mA h cm-2 .

Ultrahigh Rate and Long-Life Sodium-Ion Batteries Enabled by Engineered Surface and Near-Surface Reactions.

To achieve the high-power sodium-ion batteries, the solid-state ion diffusion in the electrode materials is a highly concerned issue and needs to be solved. In this study, a simple and effective strategy is reported to weaken and degrade this process by engineering the intensified surface and near-surface reactions, which is realized by making use of a sandwich-type nanoarchitecture composed of graphene as electron channels and few-layered MoS2 with expanded interlayer spacing. The unique 2D sheet-shaped hierarchical structure is capable of shortening the ion diffusion length, while the few-layered MoS2 with expanded interlayer spacing has more accessible surface area and the decreased ion diffusion resistance, evidenced by the smaller energy barriers revealed by the density functional theory calculations. Benefiting from the shortened ion diffusion distance and enhanced electron transfer capability, a high ratio of surface or near-surface reactions is dominated at a high discharge/charge rate. As such, the composites exhibit the high capacities of 152 and 93 mA h g-1 at 30 and 50 A g-1 , respectively. Moreover, a high reversible capacity of 684 mA h g-1 and an excellent cycling stability up to 4500 cycles can be delivered. The outstanding performance is attributed to the engineered structure with increased contribution of surface or near-surface reactions.

High-Stacking-Density, Superior-Roughness LDH Bridged with Vertically Aligned Graphene for High-Performance Asymmetric Supercapacitors.

The high-performance electrode materials with tuned surface and interface structure and functionalities are highly demanded for advanced supercapacitors. A novel strategy is presented to conFigure high-stacking-density, superior-roughness nickel manganese layered double hydroxide (LDH) bridged by vertically aligned graphene (VG) with nickel foam (NF) as the conductive collector, yielding the LDH-NF@VG hybrids for asymmetric supercapacitors. The VG nanosheets provide numerous electron transfer channels for quick redox reactions, and well-developed open structure for fast mass transport. Moreover, the high-stacking-density LDH grown and assembled on VG nanosheets result in a superior hydrophilicity derived from the tuned nano/microstructures, especially microroughness. Such a high stacking density with abundant active sites and superior wettability can be easily accessed by aqueous electrolytes. Benefitting from the above features, the LDH-NF@VG can deliver a high capacitance of 2920 F g-1 at a current density of 2 A g-1 , and the asymmetric supercapacitor with the LDH-NF@VG as positive electrode and activated carbon as negative electrode can deliver a high energy density of 56.8 Wh kg-1 at a power density of 260 W kg-1 , with a high specific capacitance retention rate of 87% even after 10 000 cycles.

Polystyrene sphere-mediated ultrathin graphene sheet-assembled frameworks for high-power density Li-O2 batteries.

Free-standing, polystyrene sphere-mediated ultrathin graphene sheet-assembled aerogels (PGA) with open and interconnected porous frameworks were configured, exhibiting high energy density and high power density as a binder-free cathode for Li-O2 batteries.

Micro-sized porous carbon spheres with ultra-high rate capability for lithium storage.

Biomass-derived carbon materials, as one type of promising anode material for lithium ion batteries (LIBs), have demonstrated intrinsic potential and superiority. Here, we report a facile and efficient approach to fabricate micro-sized porous carbon spheres (PCSs) by an integrated procedure of enzymolysis, pre-oxidation, and carbonization. Benefiting from the uniquely abundant pore accessiblity, the PCSs exhibit an ultra-high rate capability with a value of 150 mA h g(-1) at an ultrafast charge/discharge current density of 20 A g(-1), and they take only ca. 27 s to be fully charged. It is believed that the uniquely porous structure can shorten the transport paths and further enhance the rapid transport of the electrolytes and Li ions on the surface and within the electrode materials. The low cost and easy large-scale preparation of the PCS electrodes, as well as the superior high rate capability would open up an opportunity to develop high rate lithium ion batteries.