Na-metal batteries are considered as the promising alternative candidate for Li-ion battery beneficial from the wide availability and low cost of sodium, high theoretical specific capacity, and high energy density based on the plating/stripping processes and lowest electrochemical potential. For Na-metal batteries, the crucial problem on metallic Na is one of the biggest challenges. Mossy or dendritic growth of Na occurs in the repetitive Na stripping/plating process with an unstable solid electrolyte interphase layer of nonuniform ionic flux, which can not only lead to the low Coulombic efficiency, but also can create short circuit risks, resulting in possible burning or explosion. In this communication, the atomic layer deposition of Al O coating is first demonstrated for the protection of metallic Na anode for Na-metal batteries. By protecting Na foil with ultrathin Al O layer, the dendrites and mossy Na formation have been effectively suppressed and lifetime has been significantly improved. Furthermore, the thickness of protective layer has been further optimized with 25 cycles of Al O layer presenting the best performance over 500 cycles. The novel design of atomic layer deposition protected metal Na anode may bring in new opportunities to the realization of the next-generation high energy-density Na metal batteries.
Metallic Na anode is considered as a promising alternative candidate for Na ion batteries (NIBs) and Na metal batteries (NMBs) due to its high specific capacity, and low potential. However, the unstable solid electrolyte interphase layer caused by serious corrosion and reaction in electrolyte will lead to big challenges, including dendrite growth, low Coulombic efficiency and even safety issues. In this paper, we first demonstrate the inorganic-organic coating via advanced molecular layer deposition (alucone) as a protective layer for metallic Na anode. By protecting Na anode with controllable alucone layer, the dendrites and mossy Na formation have been effectively suppressed and the lifetime has been significantly improved. Moreover, the molecular layer deposition alucone coating shows better performances than the atomic layer deposition AlO coating. The novel design of molecular layer deposition protected Na metal anode may bring in new opportunities to the realization of the next-generation high energy-density NIBs and NMBs.
We apply perturbative effective mass theory as a broadly applicable theoretical model for quantum confinement (QC) in all Si and Ge nanostructures including quantum wells (QWs), wires (Q-wires) and dots (QDs). Within the limits of strong, medium, and weak QC, valence and conduction band edge energy levels (VBM and CBM) were calculated as a function of QD diameters, QW thicknesses and Q-wire diameters. Crystalline and amorphous quantum systems were considered separately. Calculated band edge levels with strong, medium and weak QC models were compared with experimental VBM and CBM reported from X-ray photoemission spectroscopy (XPS), X-ray absorption spectroscopy (XAS) or photoluminescence (PL). Experimentally, the dimensions of the nanostructures were determined directly, by transmission electron microscopy (TEM), or indirectly, by x-ray diffraction (XRD) or by XPS. We found that crystalline materials are best described by a medium confinement model, while amorphous materials exhibit strong confinement regardless of the dimensionality of the system. Our results indicate that spatial delocalization of the hole in amorphous versus crystalline nanostructures is the important parameter determining the magnitude of the band gap expansion, or the strength of the quantum confinement. In addition, the effective masses of the electron and hole are discussed as a function of crystallinity and spatial confinement.
Carbonate-based electrolytes demonstrate safe and stable electrochemical performance in lithium-sulfur batteries. However, only a few types of sulfur cathodes with low loadings can be employed and the underlying electrochemical mechanism of lithium-sulfur batteries with carbonate-based electrolytes is not well understood. Here, we employ in operando X-ray absorption near edge spectroscopy to shed light on a solid-phase lithium-sulfur reaction mechanism in carbonate electrolyte systems in which sulfur directly transfers to Li2S without the formation of linear polysulfides. Based on this, we demonstrate the cyclability of conventional cyclo-S8 based sulfur cathodes in carbonate-based electrolyte across a wide temperature range, from −20 °C to 55 °C. Remarkably, the developed sulfur cathode architecture has high sulfur content (>65 wt%) with an areal loading of 4.0 mg cm−2. This research demonstrates promising performance of lithium-sulfur pouch cells in a carbonate-based electrolyte, indicating potential application in the future.
The role of quantum confinement (QC) in Si and Ge nanostructures (NSs) including quantum dots, quantum wires, and quantum wells is assessed under a wide variety of fabrication methods in terms of both their structural and optical properties. Structural properties include interface states, defect states in a matrix material, and stress, all of which alter the electronic states and hence the measured optical properties. We demonstrate how variations in the fabrication method lead to differences in the NS properties, where the most relevant parameters for each type of fabrication method are highlighted. Si embedded in, or layered between, SiO 2 , and the role of the sub-oxide interface states embodies much of the discussion. Other matrix materials include Si 3 N 4 and Al 2 O 3. Si NSs exhibit a complicated optical spectrum, because the coupling between the interface states and the confined carriers manifests with varying magnitude depending on the dimension of confinement. Ge NSs do not produce well-defined luminescence due to confined carriers, because of the strong influence from oxygen vacancy defect states. Variations in Si and Ge NS properties are considered in terms of different theoretical models of QC (effective mass approximation, tight binding method, and pseudopotential method). For each theoretical model, we discuss the treatment of the relevant experimental parameters. V
A thin and adjustable Li3PS4 (LPS) solid‐state electrolyte protection layer on the surface of Li is proposed to address the dynamic plating/stripping process of Li metal. The LPS interlayer is formed by an in situ and self‐limiting reaction between P4S16 and Li in N‐methyl‐2‐pyrrolidone. By increasing the concentration of P4S16, the thickness of the LPS layer can be adjusted up to 60 nm. Due to the high ionic conductivity and low electrochemical activity of Li3PS4, the intimate protection layer of LPS can not only prevent the formation of Li dendrites, but also reduces parasitic side reactions and improves the electrochemical performance. As a result, symmetric cells with the LPS protection layer can deliver stable Li plating/stripping for 2000 h. Full cells assembled with the LPS‐protected Li exhibit two times higher capacity retention in Li–S batteries (≈800 mAh g−1) at 5 A g−1 for over 400 cycles compared to their bare Li counterparts. Furthermore, high rate performances can be achieved with Li‐LPS/LiCoO2 cells, which are capable of cycling at rates as high as 20 C. This innovative and scalable approach to stabilizing the Li anode can serve as a basis for the development of next‐generation high‐performance lithium‐metal batteries.
The solid electrolyte interphase (SEI) layer is one of the key factors for Li metal anode affecting the Li-deposition behavior and electrochemical performances. However, the fabrication of artificial SEI layers with precisely controlled composition, thickness, and mechanical properties is still challenging and difficult to be realized. In this study, we demonstrate an SEI-inspired dual protective layer for Li metal anode with highly controllable structures and robust mechanical properties (the organic alucone as the outer layer and inorganic Al 2 O 3 as the inner layer), which is deposited by atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques. The dual-layer protected Li anode displays significantly enhanced electrochemical performances, suppressed mossy/dead Li formation, and robust properties during the plating/stripping process. It is believed that our design of dual-layer protected Li metal anode by ALD and MLD opens up new opportunities for the realization of next-generation high-energy-density Li metal batteries.
Li metal is a promising anode material for all‐solid‐state batteries, owing to its high specific capacity and low electrochemical potential. However, direct contact of Li metal with most solid‐state electrolytes induces severe side reactions that can lead to dendrite formation and short circuits. Moreover, Li metal is unstable when exposed to air, leading to stringent processing requirements. Herein, it is reported that the Li3PS4/Li interface in all‐solid‐state batteries can be stabilized by an air‐stable LixSiSy protection layer that is formed in situ on the surface of Li metal through a solution‐based method. Highly stable Li cycling for over 2000 h in symmetrical cells and a lifetime of over 100 cycles can be achieved for an all‐solid‐state LiCoO2/Li3PS4/Li cell. Synchrotron‐based high energy X‐ray photoelectron spectroscopy in‐depth analysis demonstrates the distribution of different components within the protection layer. The in situ formation of an electronically insulating LixSiSy protection layer with highly ionic conductivity provides an effective way to prevent Li dendrite formation in high‐energy all‐solid‐state Li metal batteries.
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