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Direct formation of ultra-small nanoparticles on carbon supports by rapid high temperature synthesis method offers new opportunities for scalable nanomanufacturing and the synthesis of stable multi-elemental nanoparticles. However, the underlying mechanisms affecting the dispersion and stability of nanoparticles on the supports during high temperature processing remain enigmatic. In this work, we report the observation of metallic nanoparticles formation and stabilization on carbon supports through in situ Joule heating method. We find that the formation of metallic nanoparticles is associated with the simultaneous phase transition of amorphous carbon to a highly defective turbostratic graphite (T-graphite). Molecular dynamic (MD) simulations suggest that the defective T-graphite provide numerous nucleation sites for the nanoparticles to form. Furthermore, the nanoparticles partially intercalate and take root on edge planes, leading to high binding energy on support. This interaction between nanoparticles and T-graphite substrate strengthens the anchoring and provides excellent thermal stability to the nanoparticles. These findings provide mechanistic understanding of rapid high temperature synthesis of metal nanoparticles on carbon supports and the origin of their stability. Metal nanoparticle-decorated carbon supports are vital for many applications, ranging from energy storage and catalysis to filtration and environmental remedies. Here, using real-time electron microscopy of a single carbon nanofiber during Joule heating, the authors report atomistic mechanisms responsible for nucleation and stabilization of nanoparticles on amorphous carbon supports. [ABSTRACT FROM AUTHOR]

Despite significant interest toward solid‐state electrolytes owing to their superior safety in comparison to liquid‐based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high‐power density batteries. Here, a novel quasi‐solid Li+ ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm−2 at room temperature. The cycling overpotential is dropped by 75% in comparison to BP‐free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li+ ions around (trifluoromethanesulfonyl)imide (TFSI−) pairs and ethylene‐oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li+ transport through the polymer host. Density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li+ ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid‐state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long‐life cycling. [ABSTRACT FROM AUTHOR]

Understanding the behavior of confined matter within Van der Waals (VdW) materials is complicated due to the interplay of various factors, including the VdW interaction between the interlayers, the layer interaction with the matter, and the bending strain energy of the layers to accommodate encapsulation. Herein, new insight on the magnitude of pressure and density of water entrapped within confined spaces in VdW materials is provided. This is accomplished by studying the plasmon excitation of water encapsulated between two sheets of graphene membranes in an aberration‐corrected scanning transmission electron microscope. The results indicate ≈12% maximum increase in the density of water under tight graphene encasement, where pressure as high as 400 MPa is expected. The pressure estimation from theoretical analysis considering the effect of VdW forces, Laplace pressure, and strain energy is in agreement with the experimental results. The findings of this work open new opportunities to explore the local physical state of not only water but also other liquid materials under high pressure with imaging and analytical resolutions never achieved before. [ABSTRACT FROM AUTHOR]

Abstract: Dendritic growth of lithium (Li) has severely impeded the practical application of Li‐metal batteries. Herein, a 3D conformal graphene oxide nanosheet (GOn) coating, confined into the woven structure of a glass fiber separator, is reported, which permits facile transport of Li‐ions thought its structure, meanwhile regulating the Li deposition. Electrochemical measurements illustrate a remarkably enhanced cycle life and stability of the Li‐metal anode, which is explained by various microscopy and modeling results. Utilizing scanning electron microscopy, focused ion beam, and optical imaging, the formation of an uniform Li film on the electrode surface in the case of GO‐modified samples is revealed. Ab initio molecular dynamics (AIMD) simulations suggest that Li‐ions initially get adsorbed to the lithiophilic GOn and then diffuse through defect sites. This delayed Li transfer eliminates the “tip effect” leading to a more homogeneous Li nucleation. Meanwhile, CC bonds rupture observed in the GO during AIMD simulations creates more pathways for faster Li‐ions transport. In addition, phase‐field modeling demonstrates that mechanically rigid GOn coating with proper defect size (smaller than 25 nm) can physically block the anisotropic growth of Li. This new understanding is a significant step toward the employment of 2D materials for regulating the Li deposition. [ABSTRACT FROM AUTHOR]

Lithium metal is a highly desirable anode material for lithium batteries due to its extremely high theoretical capacity (3860 mA h g−1), low potential (−3.04 V versus standard hydrogen electrode), and low density (0.534 g cm−3). However, dendrite growth during cycling and low coulombic efficiency, resulting in safety hazards and fast battery fading, are huge barriers to commercialization. Herein, we used atomic layer deposition (ALD) to prepare conformal, ultrathin aluminum oxide coatings on lithium. We investigated the growth mechanism during Al2O3 ALD on lithium by in situ quartz crystal microbalance and found larger growth than expected during the initial cycles. We also discovered that the ALD Al2O3 enhances the wettability of the Li surface towards both carbonate and ether electrolytes, leading to uniform and dense SEI formation and reduced electrolyte consumption during battery operation. Scanning electron microscopy verified that the bare Li surfaces become rough and dendritic after electrochemical cycling, whereas the ALD Al2O3 coated Li surfaces remain smooth and uniform. Analysis of the Li surfaces after cycling using X-ray photoelectron spectroscopy and in situ transmission electron microscopy revealed that the ALD Al2O3 coating remains intact during electrochemical cycling, and that Li ions diffuse through the coating and deposit on the underlying Li. Coin cell testing demonstrated more than two times longer cycling life for the ALD Al2O3 protected Li, and a coulombic efficiency as high as ∼98% at a practical current rate of 1 mA cm−2. More significantly, when the electrolyte volume was reduced from 20 to 5 μL, the stabilizing effect of the ALD coating became even more pronounced and the cycling life was around four times longer. These results indicate that ALD Al2O3 coatings are a promising strategy to stabilize Li anodes for high performance energy storage devices such as Li–S batteries. [ABSTRACT FROM AUTHOR]

The progress on sodium-ion battery technology faces many grand challenges, one of which is the considerably lower rate of sodium insertion/deinsertion in electrode materials due to the larger size of sodium (Na) ions and complicated redox reactions compared to the lithium-ion systems. Here, it is demonstrated that sodium ions can be reversibly stored in Zn-Sb intermetallic nanowires at speeds that can exceed 295 nm s−1. Remarkably, these values are one to three orders of magnitude higher than the sodiation rate of other nanowires electrochemically tested with in situ transmission electron micro­scopy. It is found that the nanowires display about 161% volume expansion after the first sodiation and then cycle with an 83% reversible volume expansion. Despite their massive expansion, the nanowires can be cycled without any cracking or facture during the ultrafast sodiation/desodiation process. In addition, most of the phases involved in the sodiation/desodiation process possess high electrical conductivity. More specifically, the NaZnSb exhibits a layered structure, which provides channels for fast Na+ diffusion. This observation indicates that Zn-Sb intermetallic nanomaterials offer great promise as high rate and good cycling stability anodic materials for the next generation of sodium-ion batteries. [ABSTRACT FROM AUTHOR]

Commercial poly methyl methacrylate (PMMA)-based cement is currently used in the field of orthopedics. However, it suffers from lack of bioactivity, mechanical weakness, and monomer toxicity. In this study, a PMMA-based cement nanocomposite reinforced with hydroxyapatite (HA) nanofibers and two-dimensional (2D) magnesium phosphate MgP nanosheets was synthesized and optimized in terms of mechanical property and cytocompatibility. The HA nanofibers and the MgP nanosheets were synthesized using a hydrothermal homogeneous precipitation method and tuning the crystallization of the sodium-magnesium-phosphate ternary system, respectively. Compressive strength and MTT assay tests were conducted to evaluate the mechanical property and the cytocompatibility of the PMMA-HA-MgP nanocomposites prepared at different ratios of HA and MgP. To optimize the developed nanocomposites, the standard response surface methodology (RSM) design known as the central composite design (CCD) was employed. Two regression models generated by CCD were analyzed and compared with the experimental results, and good agreement was observed. Statistical analysis revealed the significance of both factors, namely, the HA nanofibers and the MgP nanosheets, in improving the compressive strength and cell viability of the PMMA-MgP-HA nanocomposite. Finally, it was demonstrated that the HA nanofibers of 7.5% wt and the MgP nanosheets of 6.12% wt result in the PMMA-HA-MgP nanocomposite with the optimum compressive strength and cell viability. [ABSTRACT FROM AUTHOR]

Widespread application of Li‐ion batteries (LIBs) in large‐scale transportation and grid storage systems requires highly stable and safe performance of the batteries in prolonged and diverse service conditions. Oxygen release from oxygen‐containing positive electrode materials is one of the major structural degradations resulting in rapid capacity/voltage fading of the battery and triggering the parasitic thermal runaway events. Herein, the authors summarize the recent progress in understanding the mechanisms of the oxygen release phenomena and correlative structural degradations observed in four major groups of cathode materials: layered, spinel, olivine, and Li‐rich cathodes. In addition, the engineering and materials design approaches that improve the structural integrity of the cathode materials and minimize the detrimental O2 evolution reaction are summarized. The authors believe that this review can guide researchers on developing mitigation strategies for the design of next‐generation oxygen‐containing cathode materials where the oxygen release is no longer a major degradation issue. [ABSTRACT FROM AUTHOR]

LiCoO2 is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from LixCoO2 particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of LixCoO2. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O2 formation more effectively due to the strong COcathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes. [ABSTRACT FROM AUTHOR]

Electronic properties of silicon, the most important semiconductor material, are controlled through doping. The range of achievable properties can be extended by hyperdoping, i.e., doping to concentrations beyond the nominal equilibrium solubility of the dopant. Here, hyperdoping is achieved in a laser pyrolysis reactor capable of providing nonequilibrium conditions, where doping is governed by kinetics rather than thermodynamics. High resolution scanning transmission electron microscopy (TEM) with energy‐dispersive X‐ray spectroscopy shows that the boron atom distribution in the hyperdoped nanoparticles is relatively uniform. The hyperdoped nanoparticles demonstrate tunable localized surface plasmon resonance (LSPR) and are stable in air for periods of at least one year. The hyperdoped nanoparticles are also stable upon annealing at temperatures up to 600 °C. Furthermore, boron hyperdoping does not change the diamond cubic crystal structure of silicon, as demonstrated in detail by high flux synchrotron X‐ray diffraction and pair distribution function (PDF) analysis, supported by high‐resolution TEM analysis. Boron‐hyperdoped silicon nanocrystals produced by laser pyrolysis of silane and diborane maintain the crystal structure of silicon with uniformly distributed boron, revealed by high‐resolution scanning transmission electron microscopy and high flux synchrotron X‐ray diffraction with pair distribution function analysis. As‐synthesized nanoparticles with 0.4–42.5 atom percent boron exhibit stable and tunable localized surface plasmon resonance at mid‐infrared wavelengths. [ABSTRACT FROM AUTHOR]