Passivation Layers in Mg-Metal Batteries: Robust Interphases for Li-Metal Batteries.

In advanced batteries, interphases serve as the key component in stabilizing the electrolyte with reactive electrode materials far beyond thermodynamic equilibria. While an active interphase facilitates the transport of working ions, an inactive interphase obstructs ion flow, constituting the primary barrier to the realization of battery chemistries. Here, a successful transformation of a traditionally inactive passivating layer on Mg-metal anode, characteristic of Mg-metal batteries with typical carbonate electrolytes, into an active and robust interphase in the Li-metal scenario is presented. By further strategically designing magnesiated Li+ electrolytes, the in situ development of this resilient interphase on Li-metal anodes, imparting enduring stability to Li-metal batteries with nickel-rich cathodes is induced. It is identified that the strong affinity between Mg2+ and anions in magnesiated Li+ electrolytes assembles ionic clusters with a bias for reducibility, thereby catalyzing the creation of anion-derived interphases rich in inorganic constituents. The prevalence of ionic clusters induced by magnesiation of electrolytes has brought properties only available in high-concentration electrolytes, suggesting a fresh paradigm of tailing electrolytes for highly reversible LMBs.

Peptide Gel Electrolytes for Stabilized Zn Metal Anodes.

The rechargeable aqueous Zn ion battery (AZIB) is considered a promising candidate for future energy storage applications due to its intrinsic safety features and low cost. However, Zn dendrites and side reactions (e.g., corrosion, hydrogen evolution reaction, and inactive side product (Zn hydroxide sulfate) formation) at the Zn metal anode have been serious obstacles to realizing a satisfactory AZIB performance. The application of gel electrolytes is a common strategy for suppressing these problems, but the normally used highly cross-linked polymer matrix (e.g., polyacrylamide (PAM)) brings additional difficulties for battery assembly and recycling. Herein, we have developed a gel electrolyte for Zn metal anode stabilization, where a peptide matrix, a highly biocompatible material, is used for gel construction. Various experiments and simulations elucidate the sulfate anion-assisted self-assembly gel formation and its effect in stabilizing Zn metal anodes. Unlike polymer gel electrolytes, the peptide gel electrolyte can reversibly transform between gel and liquid states, thus facilitating the gel-involved battery assembly and recycling. Furthermore, the peptide gel electrolyte provides fast Zn ion diffusion (comparable to conventional liquid electrolyte) while suppressing side reactions and dendrite growth, thus achieving highly stable Zn metal anodes as validated in various cell configurations. We believe that our concept of gel electrolyte design will inspire more future directions for Zn metal anode protection based on gel electrolyte design.

AgxZny Protective Coatings with Selective Zn2+/H+ Binding Enable Reversible Zn Anodes.

Zinc (Zn) metal anodes suffer from the dendrite growth and hydrogen evolution reaction (HER) in classical aqueous electrolytes, which severely limit their lifespan. We propose a rational design of AgxZny protective coatings with selective binding to Zn2+ against H+ to simultaneously regulate the Zn growth pattern and the HER kinetics. We further demonstrate that by tuning the composition of the AgxZny coating the Zn deposition behavior can be readily tuned from the conventional plating/stripping (on Zn-AgZn3 coating) to alloying/dealloying (on Ag-AgZn coating), resulting in precise control of the Zn growth pattern. Moreover, the synergy of Ag and Zn further suppresses the competitive HER. As a result, the modified Zn anodes possess a significantly enhanced lifespan. This work provides a new strategy for enhancing the stability of Zn and potentially other metal anodes by precisely manipulating the binding strength of protons and metal charge carriers in aqueous batteries.

Preferential Pyrolysis Construction of Carbon Anodes with 8400†h Lifespan for High-Energy-Density K-ion Batteries.

Carbonaceous materials are promising anodes for practical potassium-ion batteries, but fail to meet the requirements for durability and high capacities at low potentials. Herein, we constructed a durable carbon anode for high-energy-density K-ion full cells by a preferential pyrolysis strategy. Utilizing S and N volatilization from a π-π stacked supermolecule, the preferential pyrolysis process introduces low-potential active sites of sp2 hybridized carbon and carbon vacancies, endowing a low-potential "vacancy-adsorption/intercalation" mechanism. The as-prepared carbon anode exhibits a high capacity of 384.2 mAh g-1 (90 % capacity locates below 1 V vs. K/K+ ), which contributes to a high energy density of 163 Wh kg-1 of K-ion full battery. Moreover, abundant vacancies of carbon alleviate volume variation, boosting the cycling stability over 14 000 cycles (8400 h). Our work provides a new synthesis approach for durable carbon anodes of K-ion full cells with high energy densities.

Effects of stem cell-derived exosome therapy on erectile dysfunction: a systematic review and meta-analysis of preclinical studies.

Introduction: Erectile dysfunction (ED) is a common disease among elderly men, and novel therapy methods are needed for drug-refractory ED. As an extracellular vesicle, stem cell-derived exosomes displayed erectile function improvement in rat ED models in some preclinical studies. However, the therapeutic efficacy has not been comprehensively evaluated. Aim: To study the therapeutic effects of stem cell-derived exosomes on ED in preclinical studies and to investigate the potential mechanisms responsible for the efficacy. Methods: The systematic literature search was conducted in Web of Science, PubMed, and Embase to retrieve studies utilizing stem cell-derived exosomes for ED treatment. We extracted data of intracavernous pressure/mean artery pressure (ICP/MAP), and cavernosum structural changes in rat ED models before and after stem cell-derived exosome therapy. RevMan 5.3 was used to perform meta-analyses of ICP/MAP and cavernosum microstructural changes. Publication bias was assessed with the Egger test and funnel plot by Stata 15.0 (StataCorp). Main Outcome Measures: Outcomes included ICP/MAP, smooth muscle, and endothelial markers-such as the ratio of smooth muscle to collagen and the expression of α-SMA (alpha smooth muscle actin), CD31 (cluster of differentiation 31), nNOS and eNOS (neuronal and endothelial nitric oxide synthase), TGF-ß1 (transforming growth factor ß1), and caspase 3 protein-to evaluate erectile function and microstructural changes. Forest plots of effect sizes were performed. Results: Of 146 studies retrieved, 11 studies were eligible. Pooled analysis showed that stem cell-derived exosomes ameliorated damaged ICP/MAP (standardized mean difference, 3.68; 95% CI, 2.64-4.72; P < .001) and structural changes, including the ratio of smooth muscle to collagen and the expression of α-SMA, CD31, nNOS, eNOS, TGF-ß1, and caspase 3 protein. Subgroup analysis indicated that exosome type and ED model type made no difference to curative effects. Conclusion: This meta-analysis suggests the therapeutic efficacy of stem cell-derived exosomes for ED. Exosomes may restore erectile function by optimizing cavernosum microstructures.

Prediction of Ki-67 of Invasive Ductal Breast Cancer Based on Ultrasound Radiomics Nomogram.

PURPOSE: The objective of this research was to develop and validate an ultrasound-based radiomics nomogram for the pre-operative assessment of Ki-67 in breast cancer (BC). MATERIALS AND METHODS: From December 2016 to December 2018, 515 patients with invasive ductal breast cancer who received two-dimensional (2D) ultrasound and Ki-67 examination were studied and analyzed retrospectively. The dataset was distributed at random into a training cohort (n = 360) and a test cohort (n = 155) in the ratio of 7:3. Each tumor region of interest was defined based on 2D ultrasound images and radiomics features were extracted. ANOVA, maximum correlation minimum redundancy (mRMR) algorithm, and minimum absolute shrinkage and selection operator (LASSO) were performed to pick features, and independent clinical predictors were integrated with radscore to construct the nomogram for predicting Ki-67 index by univariate and multivariate logistic regression analysis. The performance and utility of the models were evaluated by plotting receiver operating characteristic (ROC) curves, decision curve analysis (DCA), and calibration curves. RESULTS: In the testing cohort, the area under the receiver characteristic curve (AUC) of the nomogram was 0.770 (95% confidence interval, 0.690-0.860). In both cohorts, the nomogram outperformed both the clinical model and the radiomics model (P < .05 according to the DeLong test). The analysis of DCA proved that the model has clinical utility. CONCLUSIONS: The nomogram based on 2D ultrasound images offered an approach for predicting Ki-67 in BC.

MoS2 -Mediated Epitaxial Plating of Zn Metal Anodes.

Metal-based anodes (Li, Zn, etc.) are regarded as promising solutions for next-generation advanced batteries due to their high theoretical specific capacities. However, most of these metal anodes suffer from dendrite growth, which severely restricts their practical applications. Recently, epitaxial anode metal deposition by choosing a suitable substrate has received tremendous attention as an effective strategy to suppress dendrites. However, the epitaxial relationship between plated metal and the substrate has been a subject of debate. Herein, large-area, mono-orientated 2D material (MoS2 ) is used, for the first time, to electrodeposit truly epitaxial Zn anodes. The continuous (without edges) mono-orientated MoS2 films are shown to be an effective strategy for suppressing metal dendrites. In addition, the epitaxial nature of the electrodeposited Zn anode is proven by pole figure analysis, which provides the first demonstration of truly epitaxial Zn anode growth over large area as metal anode protection strategy through epitaxy.

A Sustainable NH4 + Ion Battery by Electrolyte Engineering.

Aqueous ammonium ion battery is a promising sustainable energy storage system. However, the side reactions originating from electrolytes (the water decomposition and host material dissolution) preclude its practical applications. Unlike the metal-based aqueous batteries, the idea of "ultrahigh concentrated electrolyte" is not feasible due to the strong hydrolysis of ammonium ions. Therefore, we propose an effective and sustainable strategy for the water hydrogen bond network modulation by adding sucrose into the electrolytes. The sucrose can form sucrose-water hydrogen bond networks to break the continuous water hydrogen bond network, thereby inhibiting water decomposition significantly. Moreover, the weak hydrogen bond interaction between ammonium and sucrose facilitates rapid ion migration, leading to an improved ionic conductivity. This work presents a new electrolyte modulating strategy for the practical application of aqueous ammonium ion batteries.

Co-Solvent Electrolyte Engineering for Stable Anode-Free Zinc Metal Batteries.

Anode-free metal batteries can in principle offer higher energy density, but this requires them to have extraordinary Coulombic efficiency (>99.7%). Although Zn-based metal batteries are promising for stationary storage, the parasitic side reactions make anode-free batteries difficult to achieve in practice. In this work, a salting-in-effect-induced hybrid electrolyte is proposed as an effective strategy that enables both a highly reversible Zn anode and good stability and compatibility toward various cathodes. The as-prepared electrolyte can also work well under a wide temperature range (i.e., from -20 to 50 °C). It is demonstrated that in the presence of propylene carbonate, triflate anions are involved in the Zn2+ solvation sheath structure, even at a low salt concentration (2.14 M). The unique solvation structure results in the reduction of anions, thus forming a hydrophobic solid electrolyte interphase. The waterproof interphase along with the decreased water activity in the hybrid electrolyte effectively prevents side reactions, thus ensuring a stable Zn anode with an unprecedented Coulombic efficiency (99.93% over 500 cycles at 1 mA cm-2). More importantly, we design an anode-free Zn metal battery that exhibits excellent cycling stability (80% capacity retention after 275 cycles at 0.5 mA cm-2). This work provides a universal strategy to design co-solvent electrolytes for anode-free Zn metal batteries.

Three-Dimensional Ti3C2Tx MXene-Prussian Blue Hybrid Microsupercapacitors by Water Lift-Off Lithography.

The construction of electrochemical energy-storage devices by scalable thin-film microfabrication methods with high energy and power density is urgently needed for many emerging applications. Herein, we demonstrate an in-plane hybrid microsupercapacitor with a high areal energy density by employing a battery-type CuFe-Prussian blue analogue (CuFe-PBA) as the positive electrode and pseudocapacitive titanium carbide MXene (Ti3C2Tx) as the negative electrode. A three-dimensional lignin-derived laser-induced graphene electrode was prepared as the substrate by laser exposure combined with an environmentally friendly water lift-off lithography. The designed hybrid device achieved enhanced electrochemical performance thanks to the ideal match of the two types of high-rate performance materials in proton-based electrolytes and the numerous electrochemically active sites. In particular, the device delivers a high areal capacitance of 198 mF cm-2, a wide potential window (1.6 V), an ultrahigh rate performance (75.8 mF cm-2 retained even at a practical/high current density of 100 mA cm-2), and a competitive energy density of 70.5 and 27.6 µWh cm-2 at the power densities 0.74 and 52 mW cm-2, respectively. These results show that the Ti3C2Tx/CuFe-PBA hybrid microsupercapacitors are promising energy storage devices in miniaturized portable and wireless applications.

Controlled Deposition of Zinc-Metal Anodes via Selectively Polarized Ferroelectric Polymers.

Aqueous zinc-ion batteries are regarded as ideal candidates for stationary energy-storage systems due to their low cost and high safety. However, zinc can readily grow into dendrites, leading to limited cycling performance and quick failure of the batteries. Herein, a novel strategy is proposed to mitigate this dendrite problem, in which a selectively polarized ferroelectric polymer material (poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE))) is employed as a surface protective layer on zinc anodes. Such a polarized ferroelectric polymer layer can enable a locally concentrated zinc-ion distribution along the coated surface and thus enable the horizontal growth of zinc plates. As a result, symmetrical zinc batteries using such anodes exhibit long cycling lifespan at 0.2 mA cm-2 , 0.2 mAh cm-2 for 2000 h, and a high rate performance up to 15 mA cm-2 . Also, the full cell (including a Zn-MnO2 battery and a zinc-ion capacitor) based on this anode is demonstrated. This work provides a novel strategy to protect the zinc anode and even other metal anodes exploiting polymer ferroelectricity.

Molecular Engineering of Covalent Organic Framework Cathodes for Enhanced Zinc-Ion Batteries.

Covalent organic frameworks (COFs) are potentially promising electrode materials for electrochemical charge storage applications thanks to their pre-designable reticular chemistry with atomic precision, allowing precise control of pore size, redox-active functional moieties, and stable covalent frameworks. However, studies on the mechanistic and practical aspects of their zinc-ion storage behavior are still limited. In this study, a strategy to enhance the electrochemical performance of COF cathodes in zinc-ion batteries (ZIBs) by introducing the quinone group into 1,4,5,8,9,12-hexaazatriphenylene-based COFs is reported. Electrochemical characterization demonstrates that the introduction of the quinone groups in the COF significantly pushes up the Zn2+ storage capability against H+ and elevates the average (dis-)charge potential in aqueous ZIBs. Computational and experimental analysis further reveals the favorable redox-active sites that host Zn2+ /H+ in COF electrodes and the root cause for the enhanced electrochemical performance. This work demonstrates that molecular engineering of the COF structure is an effective approach to achieve practical charge storage performance.

Nanoporous Metal Phosphonate Hybrid Materials as a Novel Platform for Emerging Applications: A Critical Review.

Nanoporous metal phosphonates are propelling the rapid development of emerging energy storage, catalysis, environmental intervention, and biology, the performances of which touch many fundamental aspects of portable electronics, convenient transportation, and sustainable energy conversion systems. Recent years have witnessed tremendous research breakthroughs in these fields in terms of the fascinating pore properties, the structural periodicity, and versatile skeletons of porous metal phosphonates. This review presents recent milestones of porous metal phosphonate research, from the diversified synthesis strategies for controllable pore structures, to several important applications including adsorption and separation, energy conversion and storage, heterogeneous catalysis, membrane engineering, and biomaterials. Highlights of porous structure design for metal phosphonates are described throughout the review and the current challenges and perspectives for future research in this field are discussed at the end. The aim is to provide some guidance for the rational preparation of porous metal phosphonate materials and promote further applications to meet the urgent demands in emerging applications.

Evaluation of contrast-enhanced ultrasound for activity of rheumatoid arthritis: A protocol for systematic review and meta-analysis.

BACKGROUND: Contrast-enhanced ultrasound (CEUS) refers to a technique that uses contrast medium to strengthen the echo of backscatter, which can significantly improve the resolution, sensitivity and specificity of ultrasound diagnosis. As a quantitative imaging examination of blood flow signals, CEUS has allowed detection of synovial microvascularization in the joints of patients with rheumatoid arthritis (RA). However, the results of these studies have been contradictory. Therefore, the purpose of this study is to evaluate the value of CEUS in the activity of RA disease. METHODS: We will search PubMed, Embase, Cochrane Library, and CNKI from their inception to the December 20, 2020, without restrictions of language and publication status. Two investigators will independently carry out searching literature records, scanning titles and abstracts, full texts, collecting data, and assessing risk of bias. This study will only include high quality clinical cohort or case control studies. Statistical analysis was performed by using the Review Manager version 5.3 and the STATA version 14.0 (Stata Corp, College Station, TX, USA) softwares. RESULTS: This systematic review will determine the value of CEUS in RA activity scores. CONCLUSION: The results of this study will provide a useful basis for high-quality CEUS to evaluate RA activity score. SYSTEMATIC REVIEW REGISTRATION: INPLASY2020120125.

An Anode-Free Zn-MnO2 Battery.

Aqueous Zn-based batteries are attractive because of the low cost and high theoretical capacity of the Zn metal anode. However, the Zn-based batteries developed so far utilize an excess amount of Zn (i.e., thick Zn metal anode), which decreases the energy density of the whole battery. Herein, we demonstrate an anode-free design (i.e., zero-excess Zn), which is enabled by employing a nanocarbon nucleation layer. Electrochemical studies show that this design allows for uniform Zn electrodeposition with high efficiency and stability over a range of current densities and plating capacities. Using this anode-free configuration, we showcase a Zn-MnO2 battery prototype, showing 68.2% capacity retention after 80 cycles. Our anode-free design opens a new direction for implementing aqueous Zn-based batteries in energy storage systems.

Highly Stable Phosphonate-Based MOFs with Engineered Bandgaps for Efficient Photocatalytic Hydrogen Production.

Photoactive metal-organic frameworks (MOFs) represent one of the most promising materials for photocatalytic hydrogen production, but phosphonate-based MOFs have remained largely underdeveloped compared to other conventional MOFs. Herein, a photocatalyst of 1D titanium phosphonate MOF is designed through an easy and scalable stirring hydrothermal method. Homogeneous incorporation of organophosphonic linkers can narrow the bandgap, which is due to the strong electron-donating ability of the OH functional group that can efficiently shift the top of the valence band, moving the light absorption to the visible portion of the spectrum. In addition, the unique 1D nanowire topology enhances the photoinduced charge carrier transport and separation. Accordingly, the titanium phosphonate nanowires deliver remarkably enhanced photocatalytic hydrogen evolution activity under irradiation of both visible light and a full-spectrum simulator. Such concepts of engineering both nanostructures and electronic states herald a new paradigm for designing MOF-based photocatalysts.

Unprecedented Surface Plasmon Modes in Monoclinic MoO2 Nanostructures.

Developing stable plasmonic materials featuring earth-abundant compositions with continuous band structures, similar to those of typical metals, has received special research interest. Owing to their metal-like behavior, monoclinic MoO2 nanostructures have been found to support stable and intense surface plasmon (SP) resonances. However, no progress has been made on their energy and spatial distributions over individual nanostructures, nor the origin of their possibly existing specific SP modes. Here, various MoO2 nanostructures are designed via polydopamine chemistry and managed to visualize multiple longitudinal and transversal SP modes supported by the monoclinic MoO2 , along with intrinsic interband transitions, using scanning transmission electron microscopy coupled with ultrahigh-resolution electron energy loss spectroscopy. The identified geometry-dependent SP energies are tuned by either controlling the shape and thickness of MoO2 nanostructures through their well-designed chemical synthesis, or by altering their length using a developed electron-beam patterning technique. Theoretical calculations reveal that the strong plasmonic behavior of the monoclinic MoO2 is associated with the abundant delocalized electrons in the Mo d orbitals. This work not only provides a significant improvement in imaging and tailoring SPs of nonconventional metallic nanostructures, but also highlights the potential of MoO2 nanostructures for micro-nano optical and optoelectronic applications.

Single-Crystal Cobalt Phosphate Nanosheets for Biomimetic Oxygen Evolution in Neutral Electrolytes.

To improve energy conversion efficiency, the development of active electrocatalysts with similar structural features to photosynthesis II systems (PS-II), which can efficiently catalyze the oxygen evolution reaction (OER), have received great research interest. Crystalline cobalt phosphate nanosheets are designed as an efficient OER catalyst in neutral media, showing outstanding performance that even outperforms the noble RuO2 benchmark. The correlation of experimental and computational results reveals that the active sites are the edge-sharing CoO9 structural motif, akin to the molecular geometry of PS-II. This unique structure can facilitate reaction intermediate adsorption and decrease the reaction energy barrier, thus improving the OER kinetics.

Designing Nanostructured Metal-Based CO2 Reduction Electrocatalysts.

Capture and conversion of CO2 into value-added chemicals and fuels is one of the most sought-after hot points at the scientific frontier. Driven by renewable energy derived electricity, the heterogeneous electrocatalyic CO2 reduction has attracted intensive interests because of the easy manipulation and high-energy-density fuels supply. Metals with general abundance and robust ability for activating CO2 have been adopted as the core-atom for developing advanced CO2 reduction electrocatalysts. As the dramatic development of nano-technology, the nanostructured metal-based materials become promising candidates for various catalytic systems. In this Review article, a general introduction and principles applied in CO2 electroreduction are summarized and discussed. Then the proposed reaction pathways of the CO2 reduction were classified and elaborated depending on the products. The state of the art advances related to the nanostructured metallic electrocatalysts are addressed as well. At last, the remaining challenges and further prospects for the construction of new nanostructured electrocatalysts for CO2 reduction and improvement of existing ones have been presented.

When Carbon Meets CO2: Functional Carbon Nanostructures for CO2 Utilization.

Major fossil fuel consumption associated with CO2 emission and socioeconomic instability has received much concern within the global community regarding the long-term sustainability and security of these commodities. The capture, sequestration, and conversion of CO2 emissions from flue gas are now becoming familiar worldwide. Nanostructured carbonaceous materials with designed functionality have been extensively used in some key CO2 exploitation processes and techniques, because of their excellent electrical conductivity, chemical/mechanical stability, adjustable chemical compositions, and abundant active sites. This review focuses on a variety of carbonaceous materials, like graphene, carbon nanotubes, amorphous porous carbons and carbon hybrid composites, which have been demonstrated promising in CO2 capture/separation and conversion (electrocatalysis and photocatalysis) to produce value-added chemicals and fuels. Along with the discussion and concerning synthesis strategies, characterization and conversion and capture/separation techniques employed, we further elaborate the structure-performance relationships in terms of elucidating active sites, reaction mechanisms and kinetics improvement. Finally, challenges and future perspectives of these carbon-based materials for CO2 applications using well-structured carbons are remarked in detail.