Identifying the Active Sites in MoSi2@MoO3 Heterojunctions for Enhanced Hydrogen Evolution.

Developing Two-dimensional (2D) Mo-based heterogeneous nanomaterials is of great significance for energy conversion, especially in alkaline hydrogen evolution reaction (HER), however, it remains a challenge to identify the active sites at the interface due to the structure complexity. Herein, the real active sites are systematically explored during the HER process in varied Mo-based 2D materials by theoretical computational and magnetron sputtering approaches first to filtrate the candidates, then successfully combined the MoSi2 and MoO3 together through Oxygen doping to construct heterojunctions. Benefiting from the synergistic effects between the MoSi2 and MoO3, the obtained MoSi2@MoO3 exhibits an unprecedented overpotential of 72 mV at a current density of 10 mA cm-2. Density functional theory calculations uncover the different Gibbs free energy of hydrogen adsorption (ΔGH*) values achieved at the interfaces with different sites as adsorption sites. The results can facilitate the optimization of heterojunction electrocatalyst design principles for the Mo-based 2D materials.

Study of the Corrosion Behavior of Cathode Current Collector in LiFSI Electrolyte.

Cycling aging is the one of the main reasons affecting the lifetime of lithium-ion batteries and the contribution of aluminum current collector corrosion to the ageing is not fully recognized. In general, aluminum is corrosion resistant to electrolyte since a non-permeable surface film of alumina is naturally formed. However, corrosion of aluminum current collector can still occur under certain conditions such as lithium bis(fluorosulfonyl)imide (LiFSI)-based electrolyte or high voltage. Herein, we investigates the corrosion of aluminum current collector in the electrolyte of 1.2 M LiFSI in ethylene carbonate (EC) and ethyl methyl carbonate (EMC) mixed solvents. The electrochemical results shows that the corrosion current of aluminum is enhanced by cycling time and potential, which is correlated with the surface species and morphology. The formation of AlF3, which is induced by deep penetration of F- anions through surface passivation film, leads to internal volume change and the surface crack in the end. Our work will be inspiring for future development of high-energy-density and high-power-density lithium-ion batteries in which the LiFSI salt will be intensively used.

Promoting hydrophilic cupric oxide electrochemical carbon dioxide reduction to methanol via interfacial engineering modulation.

Copper-based catalysts have been extensively investigated in electrochemical carbon dioxide (CO2) reduction to promote carbon products generated by requiring multiple electron transfer. However, hydrophilic electrodes are unfavourable for CO2 mass transfer and preferentially hydrogen (H2) evolution in electrochemical CO2 reduction. In this paper, a hydrophilic cupric oxide (CuO) electrode with a grassy morphology was prepared. CuO-derived Cu was confirmed as the active site for electrochemical CO2 reduction through wettability modulation. To enhance the intrinsic catalytic activity, a metal-oxide heterogeneous interface was created by engineering modulation at the interface, involving the loading of palladium (Pd) on CuO (CuO/Pd). Both the electrochemically active area and the electron transfer rate were enhanced by Pd loading, and significantly the reduced work function further facilitated the electron transfer between the electrode surface and the electrolyte. Consequently, the CuO/Pd electrode exhibited excellent excellent performance in electrochemical CO2 reduction, achieving a 54 % Faraday efficiency at -0.65 V for methanol (CH3OH). The metal-oxide interfacial effect potentially improves the intrinsic catalytic activity of hydrophilic CuO electrodes in electrochemical CO2 reduction, providing a conducive pathway for optimizing hydrophilic oxide electrodes in this process.

Quasi-Solid-State All-V2O5 Battery.

Solid-state symmetrical battery represents a promising paradigm for future battery technology. However, its development is hindered by the deficiency of high-performance bipolar electrodes and compatible solid electrolytes. Herein, a quasi-solid-state all-V2O5 battery constructed by a binder-free carbon fabric-V2O5 nanowires@graphene (CVOG) bipolar electrode and a softly cross-linked polyethylene oxide-based solid polymer electrolyte (SPE) is reported. The synergetic effect of nano-structuring of V2O5, hierarchical conductive network, and graphene wrapping endows the CVOG electrode with boosted reaction kinetics and suppressed vanadium dissolution. The cathodic and anodic reactions of CVOG are decoupled by electrochemical analysis, conceiving the feasibility of constructing all-V2O5 full battery. In manifesting the solid-state all-V2O5 battery, the robust and elastic SPE exhibits high ionic conductivity, tight/self-adaptable electrolyte-electrode contact, and a low charge-transfer barrier. The resultant solid-state full battery exhibits a high reversible capacity of 158 mAh g-1 at 0.1 C, good capacity retention of over 61% from 0.1 C to 2 C, and remarkable cycling stability of 77% capacity retention after 1000 cycles at 1 C, which surpass other solid-state symmetrical batteries. Hence, this work provides a practice of high-performance solid-state batteries with symmetrical configuration and is constructive for next-generation battery technology.

Role of Interfacial Defects on Electro-Chemo-Mechanical Failure of Solid-State Electrolyte.

High-stress field generated by electroplating of lithium (Li) in pre-existing defects is the main reason for mechanical failure of solid-state electrolyte because it drives crack propagation in electrolyte, followed by Li filament growth inside and even internal short-circuit if the filament reaches another electrode. To understand the role of interfacial defects on mechanical failure of solid-state electrolyte, an electro-chemo-mechanical model is built to visualize distribution of stress, relative damage, and crack formation during electrochemical plating of Li in defects. Geometry of interfacial defect is found as dominating factor for concentration of local stress field while semi-sphere defect delivers less accumulation of damage at initial stage and the longest failure time for disintegration of electrolyte. Aspect ratio, as a key geometric parameter of defect, is investigated to reveal its impact on failure of electrolyte. Pyramidic defect with low aspect ratio of 0.2-0.5 shows branched region of damage near interface, probably causing surface pulverization of solid-state electrolyte, whereas high aspect ratio over 3.0 will trigger accumulation of damage in bulk electrolyte. The correction between interfacial defect and electro-chemo-mechanical failure of solid-state electrolyte is expected to provide insightful guidelines for interface design in high-power-density solid-state Li metal batteries.

Electro-Chemo-Mechanical Failure of Solid Electrolytes Induced by Growth of Internal Lithium Filaments.

Growth of lithium (Li) filaments within solid electrolytes, leading to mechanical degradation of the electrolyte and even short circuit of the cell under high current density, is a great barrier to commercialization of solid-state Li-metal batteries. Understanding of this electro-chemo-mechanical phenomenon is hindered by the challenge of tracking local fields inside the solid electrolyte. Here, a multiphysics simulation aiming to investigate evolution of the mechanical failure of the solid electrolyte induced by the internal growth of Li is reported. Visualization of local stress, damage, and crack propagation within the solid electrolyte enables examination of factors dominating the degradation process, including the geometry, number, and size of Li filaments and voids in the electrolyte. Relative damage induced by locally high stress is found to preferentially occur in the region of the electrolyte/Li interface having great fluctuations. A high number density of Li filaments or voids triggers integration of damage and crack networks by enhanced propagation. This model is built on coupling of mechanical and electrochemical processes for internal plating of Li, revealing evolution of multiphysical fields that can barely be captured by the state-of-the-art experimental techniques. Understanding mechanical degradation of solid electrolytes with the presence of Li filaments paves the way to design advanced solid electrolytes for future solid-state Li-metal batteries.

Compressive Property of Additively-Manufactured Micro-Architectures with X-Type Lattice Unit Cell.

In this paper, novel micro-architectures with X-type lattice unit cell (namely, face-centered cubic (FCC), and X-type) are constructed and prepared by additive manufacturing technology. The compression behaviors of micro-architectures are explored in detail by experimental measurement and theoretical prediction. It is found that the strength of FCC micro-lattice structure is higher than that of the X-type micro-lattice structure with the same relative density. The X-type micro-lattice structure exhibits a zero Poisson's ratio during compression deformation. In addition, the compressive strength and energy absorption efficiency of proposed micro-architectures shows a higher advantage over other previously cellular materials in a map for material selection.

Two Birds with One Stone: Using Indium Oxide Surficial Modification to Tune Inner Helmholtz Plane and Regulate Nucleation for Dendrite-free Lithium Anode.

Lithium metal has been considered as the most promising anode material due to its distinguished specific capacity of 3860 mAh g-1 and the lowest reduction potential of -3.04 V versus the Standard Hydrogen Electrode. However, the practicalization of Li-metal batteries (LMBs) is still challenged by the dendritic growth of Li during cycling, which is governed by the surface properties of the electrodepositing substrate. Herein, a surface modification with indium oxide on the copper current collector via magnetron sputtering, which can be spontaneously lithiated to form a composite of lithium indium oxide and Li-In alloy, is proposed. Thus, the growth of Li dendrites is effectively suppressed via regulating the inner Helmholtz plane modified with LiInO2 to foster the desolvation of Li-ion and induce the nucleation of Li-metal in two-dimensions through electro-crystallization with Li-In alloy. Using the In2 O3 modification, the Li-metal anode exhibits outstanding cyclic stability, and LMBs with lithium cobalt oxide cathode present excellent capacity retention (above 80% over 600 cycles). Enlightening, the scalable magnetron sputtering method reported here paves a novel way to accelerate the practical application of the Li anode in LMBs to pursue higher energy density.

Fluorine Dissolution-Induced Capacity Degradation for Fluorophosphate-Based Cathode Materials.

Na3V2(PO4)2F3 has been considered as a promising cathode material for sodium-ion batteries due to its high operating voltage and structural stability. However, the issues about poor cycling performance and lack of understanding for the capacity degradation mechanism are the major hurdle for practical application. Herein, we meticulously analyzed the evolution of the morphology, crystal structure, and bonding states of the cathode material during the cycling process. We observed that capacity degradation is closely related to the shedding of the active material from the collector caused by HF corrosion. Meanwhile, HF is produced through F anion dissolution from Na3V2(PO4)2F3 induced by trace H2O during the cycling process. The F- dissolution-induced degradation mechanism based on fluorine-containing cathode materials is proposed for the first time, providing a new insight for the understanding, modification, and performance improvement for fluorophosphate-based cathode materials.

Insight into the Critical Role of Exchange Current Density on Electrodeposition Behavior of Lithium Metal.

Due to an ultrahigh theoretical specific capacity of 3860 mAh g-1, lithium (Li) is regarded as the ultimate anode for high-energy-density batteries. However, the practical application of Li metal anode is hindered by safety concerns and low Coulombic efficiency both of which are resulted fromunavoidable dendrite growth during electrodeposition. This study focuses on a critical parameter for electrodeposition, the exchange current density, which has attracted only little attention in research on Li metal batteries. A phase-field model is presented to show the effect of exchange current density on electrodeposition behavior of Li. The results show that a uniform distribution of cathodic current density, hence uniform electrodeposition, on electrode is obtained with lower exchange current density. Furthermore, it is demonstrated that lower exchange current density contributes to form a larger critical radius of nucleation in the initial electrocrystallization that results in a dense deposition of Li, which is a foundation for improved Coulombic efficiency and dendrite-free morphology. The findings not only pave the way to practical rechargeable Li metal batteries but can also be translated to the design of stable metal anodes, e.g., for sodium (Na), magnesium (Mg), and zinc (Zn) batteries.

Fluorescent Metallacycle-Cored Amphiphilic Nanoparticles Formed by ß-Cyclodextrin-Based Host-Guest Interactions towards Cancer Theranostics.

Theranostic agents, taking the advantages of both imaging and therapeutic functions, are anticipated to be key components in the development of personalized medicine in which the therapeutic response can be real-time monitored. Herein, three metallacycles with pendent adamantane groups are prepared by coordination-driven self-assembly of PtII ligands with anticancer activities and tetraphenylethylene derivatives with emission. ß-Cyclodextrin, which shows good host-guest interactions with adamantane moieties, was added to form amphiphilic supramolecular nanoparticles with the aim to enhance the aqueous solubilities and bioactivities of these metallacycles. Moreover, when rhodamine-modified ß-cyclodextrin was used as the carrier, the release of the metallacycles from the nanoparticles could be monitored in situ through the fluorescence changes owing to the efficient fluorescence resonance energy transfer from the metallacycles to rhodamine-modified ß-cyclodextrin. In vitro and in vivo studies showed that these nanoparticles not only served as cell imaging contrast agents but also displayed improved anticancer activities, allowing them to serve as potential candidates for cancer theranostics. This study provides a simple and efficient method to prepare theranostic agents by hierarchical supramolecular self-assembly, which will pave the way for image-guided cancer therapy, targeted cancer therapy, and related biomedical fields.

Ta@Ag Porous Array with High Stability and Biocompatibility for SERS Sensing of Bacteria.

The reliable sensing of bacteria by surface-enhanced Raman scattering (SERS) technology necessitates a rational design of a substrate with high sensitivity, stability, and minimal invasion. Hence, a bimetallic Ta@Ag film with a porous array is developed by the magnetron sputtering technique and the structure could be controlled by a Ta dopant. A porous array connected by ligaments with compact granular nanoprotrusions is a fascinating substrate for SERS sensing. It makes steady SERS signals even in harsh chemical environments due to its high structural and chemical stability. The configuration of binary Ta@Ag has higher surface free energy than that of pure Ag, and the strong bactericidal activity of Ag is suppressed efficiently. Using E. coli as a model pathogen, the Ta@Ag porous film could maintain the long-term survival rate of E. coli up to 95% and a limit of SERS detection of E. coli down to 102 CFU/mL, which is measured by the standard colony-counting method. In sum, this work provides a promising strategy to fabricate a corrosion-resistant and biocompatible bimetallic Ta@Ag film with a porous array for the SERS sensing of microbial cells.

Deep Phase Transition of MoS2 for Excellent Hydrogen Evolution Reaction by a Facile C-Doping Strategy.

Metallic 1T-phase MoS2 is considered to be the ideal electrocatalyst to carry out hydrogen evolution reaction (HER) because of favorable conductivity and sufficient active site compared with 2H-phase MoS2. Nevertheless, 1T-phase MoS2 is conventionally synthesized in a complicated process, with the production of an unstable product, which hinders their practical applications. Herein, we propose a facile approach through a carbon-doping-induced phase transition to obtain highly stable 1T-2H mixed MoS2 nanosheets. The phase transition process is characterized by Raman and X-ray photoelectron spectroscopy, as well as high-resolution transmission electron microscopy images and delivers a high phase purity of ∼60% for 1T-MoS2. According to density functional theory simulations and experimental results, C-doped 1T-2H mixed MoS2 has the advantages of abundant active sites, facilitated charge transfer rate, and high activity toward HER. The obtained C-doped MoS2 exhibits a superb HER electrocatalytic performance, with a current density of 10 mA cm-2 and the overpotential as low as 40 mV in 1 M KOH solution, and brilliant stability.

Polydopamine@Gold Nanowaxberry Enabling Improved SERS Sensing of Pesticides, Pollutants, and Explosives in Complex Samples.

Surface-enhanced Raman scattering (SERS) is a promising analysis technique for detecting various analytes in complex samples due to its unique vibrational fingerprints and high signal enhancement. However, impurity interference and substrate unreliability are direct suppression factors for practical application. Herein, we synthesize polydopamine@gold (PDA@Au) nanowaxberry, where Au nanoparticles are deposited on the surface of PDA sphere with high density and uniformity. Seed-mediated synthesis is used for fabrication of nanowaxberry. Au seeds are deposited on the surface of PDA sphere, then I ion coordinating ligand is employed to form stable AuI4- complex with AuCl4-, which decreases reduction potential of AuCl4- and avails formation of shell structure. Such nanowaxberry has high density of voids and gaps in three-dimensional space, which could absorb analytes and benefit practical SERS detection. Using malachite green as a model analyte, nanowaxberry realizes highly sensitive detection with low limit of detection (1 pM) and good reproducibility (relative standard deviation of about 10%). Meanwhile, the nanowaxberry is employed for practical detection of thiram, benzidine, and 2,4-dinitrotoluene in the environmental water, juice, apple peel, and soil. The high performance makes nanowaxberry to be potentially used for pesticides detection, pollutants monitoring, and forbidden explosives sensing in complex samples.

Statistical study of ductility-dip cracking induced plastic deformation in polycrystalline laser 3D printed Ni-based superalloy.

Ductility-dip cracking in Ni-based superalloy, resulting from heat treatment, is known to cause disastrous failure, but its mechanism is still not completely clear. A statistical study of the cracking behavior as a function of crystal orientation in a laser 3D-printed DL125L Ni-based superalloy polycrystal is investigated here using the synchrotron X-ray microdiffraction. The dislocation slip system in each of the forty crystal grains adjacent to the 300 µm long crack has been analyzed through Laue diffraction peak shapes. In all these grains, edge-type geometrically necessary dislocations (GNDs) dominate, and their dislocation line directions are almost parallel to the crack plane. Based on Schmid's law, the equivalent uniaxial tensile force direction is revealed normal to the trace of the crack. A qualitative mechanism is thus proposed. Thermal tensile stress perpendicular to the laser scanning direction is elevated due to a significant temperature gradient, and thus locations in the materials where the thermal stress exceeds the yield stress undergo plastic deformation mediated by GND activations. As the dislocations slip inside the crystal grains and pile up at the grain boundaries, local strain/stress keeps increasing, until the materials in these regions fail to sustain further deformation, leading to voids formation and cracks propagation.

Enhanced resistive switching characteristics in Al2O3 memory devices by embedded Ag nanoparticles.

In this paper, Al2O3/Ag/Al2O3 sandwiched thin films were deposited by magnetron sputtering. Al2O3 thin films with embedded Ag nanoparticles (AgNPs) have been fabricated by adopting appropriate experimental parameters. The measurements on the resistive switching behaviors demonstrated that the embedded AgNPs could substantially enhance the local electric field, and effectively reduce the switching voltages, resulting in a sharply increased OFF/ON ratio up to 106 at 0.5 V. Furthermore, the cycling stability was considerably improved owing to the reduced randomness for the formation and rupture of conductive filaments (CFs). AgNPs could also contribute with movable Ag ions, and the Ti top electrode usually reacts with Al2O3 promoting the formation of oxygen vacancies. As a result, a hybrid CF with better high-temperature stability was induced. Comparatively, if the embedded Ag sublayer is smooth, the switching parameters become dispersive owing to the random formation and rupture of CFs, and the switching performance is deteriorated. A physical model was proposed to understand the effect of the embedded AgNPs.

A synchrotron study of microstructure gradient in laser additively formed epitaxial Ni-based superalloy.

Laser additive forming is considered to be one of the promising techniques to repair single crystal Ni-based superalloy parts to extend their life and reduce the cost. Preservation of the single crystalline nature and prevention of thermal mechanical failure are two of the most essential issues for the application of this technique. Here we employ synchrotron X-ray microdiffraction to evaluate the quality in terms of crystal orientation and defect distribution of a Ni-based superalloy DZ125L directly formed by a laser additive process rooted from a single crystalline substrate of the same material. We show that a disorientation gradient caused by a high density of geometrically necessary dislocations and resultant subgrains exists in the interfacial region between the epitaxial and stray grains. This creates a potential relationship of stray grain formation and defect accumulation. The observation offers new directions on the study of performance control and reliability of the laser additive manufactured superalloys.

Rectifying switching characteristics of Pt/ZnO/Pt structure based resistive memory.

40 nm thick amorphous ZnO thin films were deposited by radio frequency magnetron sputtering at room temperature and asymmetric electrical switching characteristics are observed in the macroscopic symmetric Pt/ZnO/Pt structure. The crystal structure was examined by X-ray diffraction (XRD). The chemical bonding states of ZnO resistive switching layer was investigated by X-ray photoelectron spectroscopy (XPS). Keithley 4200 semiconductor characterization system was used to measure the current-voltage (I-V) characteristics of the fabricated devices. The results reveal that a reversible resistive switching behavior between the high resistance state and the low resistance state with rectifying effects can be repeated for more than 100 dc cycles. This asymmetric electrical behavior is thought to be related to the naturally self-formed PtOx between ZnO film and the Pt bottom electrode, which introduces an energy barrier when electrons flow from top electrode towards the bottom electrode. The model of Pt/ZnO/Pt memory cell is expected to be able to alleviate the misreading error in cross-point array for high density integrations.