Si electrode failure mechanisms: (a) Material pulverization. (b) Continuous SEI growth. (c) Morphology and volume change of the entire Si electrode. Display omitted
► We reviewed recent research ...progress on Si based high performance anode for lithium ion batteries. ► We reviewed the fundamental challenges associated with large volume change in Si anode. ► Nanostructured materials design can significantly improve the cycling life of Si anode. ► The nanoscale design principles can also be extended to other battery materials that undergo large volume changes.
High energy lithium ion batteries are in demand for consumer electronics, electric-drive vehicles and grid-scale stationary energy storage. Si is of great interest since it has 10 times higher specific capacity than traditional carbon anodes. However, the poor cyclability due to the large volume change of Si upon insertion and extraction of lithium has been an impediment to its deployment. This review outlines three fundamental materials challenges associated with large volume change, and then shows how nanostructured materials design can successfully address these challenges. There have been three generations of nanostructure design, encompassing solid nanostructures such as nanowires, hollow nanostructures, and clamped hollow structures. The nanoscale design principles developed for Si can also be extended to other battery materials that undergo large volume changes.
Hollow nanostructures have shown great promise for energy storage, conversion, and production technologies. Significant efforts have been devoted to the design and synthesis of hollow nanostructures ...with diverse compositional and geometric characteristics in the past decade. However, the correlation between their structure and energy‐related performance has not been reviewed thoroughly in the literature. Here, some representative examples of designing hollow nanostructure to effectively solve the problems of energy‐related technologies are highlighted, such as lithium‐ion batteries, lithium‐metal anodes, lithium–sulfur batteries, supercapacitors, dye‐sensitized solar cells, electrocatalysis, and photoelectrochemical cells. The great effect of structure engineering on the performance is discussed in depth, which will benefit the better design of hollow nanostructures to fulfill the requirements of specific applications and simultaneously enrich the diversity of the hollow nanostructure family. Finally, future directions of hollow nanostructure design to solve emerging challenges and further improve the performance of energy‐related technologies are also provided.
Hollow nanostructures are promising candidates for various energy‐storage technologies, especially for lithium‐ion batteries, lithium‐metal anodes, lithium–sulfur batteries, supercapacitors, dye‐sensitized solar cells, electrocatalysis, and photoelectrochemical cells. In‐depth understanding about the effect of structure engineering on performance is discussed, by which the design of hollow nanostructures can be improved, to fulfill the requirements of specific applications, and simultaneously enrich the diversity of the hollow nanostructure family.
Eccrine sweat glands help to maintain homoeostasis, primarily by stabilizing body temperature. Derived from embryonic ectoderm, millions of eccrine glands are distributed across human skin and ...secrete litres of sweat per day. Their easy accessibility has facilitated the start of analyses of their development and function. Mouse genetic models find sweat gland development regulated sequentially by Wnt, Eda and Shh pathways, although precise subpathways and additional regulators require further elucidation. Mature glands have two secretory cell types, clear and dark cells, whose comparative development and functional interactions remain largely unknown. Clear cells have long been known as the major secretory cells, but recent studies suggest that dark cells are also indispensable for sweat secretion. Dark cell‐specific Foxa1 expression was shown to regulate a Ca2+‐dependent Best2 anion channel that is the candidate driver for the required ion currents. Overall, it was shown that cholinergic impulses trigger sweat secretion in mature glands through second messengers – for example InsP3 and Ca2+ – and downstream ion channels/transporters in the framework of a Na+‐K+‐Cl− cotransporter model. Notably, the microenvironment surrounding secretory cells, including acid–base balance, was implicated to be important for proper sweat secretion, which requires further clarification. Furthermore, multiple ion channels have been shown to be expressed in clear and dark cells, but the degree to which various ion channels function redundantly or indispensably also remains to be determined.
The widespread implementation of high-energy-density lithium metal batteries has long been fettered by lithium dendrite-related failure. Here we report a new strategy to address the issue of dendrite ...growth by a polyimide-coating layer with vertical nanoscale channels of high aspect ratio. Smooth, granular lithium metal was deposited on the modified electrode instead of typical filamentary growths. In a comparison with the bare planar electrode, the modified electrode achieved greatly enhanced Coulombic efficiency and longer cycle life. Homogeneous Li+ flux distribution above the modified electrode from the nanochannel confinement can account for a uniform Li nucleation and a nondendrite growth. We also demonstrated that the polyimide coating with microscale pores loses the confinement effects and fails to suppress lithium dendrites. This strategy of spatially defined lithium growth in vertical-aligned nanochannels provides a novel approach and a significant step toward stabilizing Li metal anodes.
Lithium metal has re-emerged as an exciting anode for high energy lithium-ion batteries due to its high specific capacity of 3860 mAh g–1 and lowest electrochemical potential of all known materials. ...However, lithium has been plagued by the issues of dendrite formation, high chemical reactivity with electrolyte, and infinite relative volume expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with lithium metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a critical fundamental scientific foundation of Li plating. Here, we study experimentally the morphology of lithium in the early stages of nucleation and growth on planar copper electrodes in liquid organic electrolyte. We elucidate the dependence of lithium nuclei size, shape, and areal density on current rate, consistent with classical nucleation and growth theory. We found that the nuclei size is proportional to the inverse of overpotential and the number density of nuclei is proportional to the cubic power of overpotential. Based on this understanding, we propose a strategy to increase the uniformity of electrodeposited lithium on the electrode surface.
Conspectus The development of next-generation lithium-based rechargeable batteries with high energy density, low cost, and improved safety is a great challenge with profound technological ...significance for portable electronics, electric vehicles, and grid-scale energy storage. Specifically, advanced lithium battery chemistries call for a paradigm shift to electrodes with high Li to host ratio based on a conversion or alloying mechanism, where the increased capacity is often accompanied by drastic volumetric changes, significant bond breaking, limited electronic/ionic conductivity, and unstable electrode/electrolyte interphase. Fortunately, the rapid progress of nanotechnology over the past decade has been offering battery researchers effective means to tackle some of the most pressing issues for next-generation battery chemistries. The major applications of nanotechnology in batteries can be summarized as follows: First, by reduction of the dimensions of the electrode materials, the cracking threshold of the material upon lithiation can be overcome, at the same time facilitating electron/ion transport within the electrode. Second, nanotechnology also provides powerful methods to generate various surface-coating and functionalization layers on electrode materials, protecting them from side reactions in the battery environment. Finally, nanotechnology gives people the flexibility to engineer each and every single component within a battery (separator, current collector, etc.), bringing novel functions to batteries that are unachievable by conventional methods. Thus, this Account aims to highlight the crucial role of nanotechnology in advanced battery systems. Because of the limited space, we will mainly assess representative examples of rational nanomaterials design with complexity for silicon and lithium metal anodes, which have shown great promise in constraining their large volume changes and the repeated solid–electrolyte interphase formation during cycling. Noticeably, the roadmap delineating the gradual improvement of silicon anodes with a span of 11 generations of materials designs developed in our group is discussed in order to reflect how nanotechnology could guide battery research step by step toward practical applications. Subsequently, we summarize efforts to construct nanostructured composite sulfur cathodes with improved electronic conductivity and effective soluble species encapsulation for maximizing the utilization of active material, cycle life, and system efficiency. We emphasize carbon-based materials and, importantly, materials with polar surfaces for sulfur entrapment. We then briefly discuss nanomaterials strategies to improve the ionic conductivity of solid polymer electrolytes by means of incorporating high-surface-area and, importantly, high-aspect-ratio secondary-phase fillers for continuous, low-tortuosity ionic transport pathways. Finally, critical innovations that have been brought to the area of grid-scale energy storage and battery safety by nanotechnology are also succinctly reviewed.
Homogeneous catalysts generally possess superior catalytic performance compared to heterogeneous catalysts. However, the issue of catalyst separation and recycling severely limits their use in ...practical applications. Single‐atom catalysts have the advantages of both homogeneous catalysts, such as “isolated sites”, and heterogeneous catalysts, such as stability and reusability, and thus would be a promising alternative to traditional homogeneous catalysts. In the hydroformylation of olefins, single‐atom Rh catalysts supported on ZnO nanowires demonstrate similar efficiency (TON≈40000) compared to that of homogeneous Wilkinson's catalyst (TON≈19000). HAADF‐STEM and infrared CO chemisorption experiments identified isolated Rh atoms on the support. XPS and XANES spectra indicate that the electronic state of Rh is almost metallic. The catalysts are about one or two orders of magnitude more active than most reported heterogeneous catalysts and can be reused four times without an obvious decline in activity.
Rhodium single‐atom catalysts supported on ZnO nanowires display olefin hydroformylation efficiency comparable to that of homogeneous Wilkinson's catalyst.
Surface-supported isolated atoms in single-atom catalysts (SACs) are usually stabilized by diverse defects. The fabrication of high-metal-loading and thermally stable SACs remains a formidable ...challenge due to the difficulty of creating high densities of underpinning stable defects. Here we report that isolated Pt atoms can be stabilized through a strong covalent metal-support interaction (CMSI) that is not associated with support defects, yielding a high-loading and thermally stable SAC by trapping either the already deposited Pt atoms or the PtO
units vaporized from nanoparticles during high-temperature calcination. Experimental and computational modeling studies reveal that iron oxide reducibility is crucial to anchor isolated Pt atoms. The resulting high concentrations of single atoms enable specific activities far exceeding those of conventional nanoparticle catalysts. This non defect-stabilization strategy can be extended to non-reducible supports by simply doping with iron oxide, thus paving a new way for constructing high-loading SACs for diverse industrially important catalytic reactions.
Nanomaterials provide many desirable properties for electrochemical energy storage devices due to their nanoscale size effect, which could be significantly different from bulk or micron-sized ...materials. Particularly, confined dimensions play important roles in determining the properties of nanomaterials, such as the kinetics of ion diffusion, the magnitude of strain/stress, and the utilization of active materials. Nanowires, as one of the representative one-dimensional nanomaterials, have great capability for realizing a variety of applications in the fields of energy storage since they could maintain electron transport along the long axis and have a confinement effect across the diameter. In this review, we give a systematic overview of the state-of-the-art research progress on nanowires for electrochemical energy storage, from rational design and synthesis, in situ structural characterizations, to several important applications in energy storage including lithium-ion batteries, lithium-sulfur batteries, sodium-ion batteries, and supercapacitors. The problems and limitations in electrochemical energy storage and the advantages in utilizing nanowires to address the issues and improve the device performance are pointed out. At the end, we also discuss the challenges and demonstrate the prospective for the future development of advanced nanowire-based energy storage devices.
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