Allen Pei

Catalytic Iridium-Based Janus Micromotors Powered by Ultralow Levels of Chemical Fuels

We describe catalytic micromotors powered by remarkably low concentrations of chemical fuel, down to the 0.0000001% level. These Janus micromotors rely on an iridium hemispheric layer for the catalytic decomposition of hydrazine in connection to SiO2 spherical particles. The micromotors are self-propelled at a very high speed (of ~20 body lengths s(-1)) in a 0.001% hydrazine solution due to osmotic effects. Such a low fuel concentration represents a 10,000-fold decrease in the level required for common catalytic nanomotors. The attractive propulsion performance, efficient catalytic energy-harvesting, environmentally triggered swarming behavior, and magnetic control of the new Janus micromotors hold considerable promise for diverse practical applications.

Bioinspired Helical Microswimmers Based on Vascular Plants

Plant-based bioinspired magnetically propelled helical microswimmers are described. The helical microstructures are derived from spiral water-conducting vessels of different plants, harnessing the intrinsic biological structures of nature. Geometric variables of the spiral vessels, such as the helix diameter and pitch, can be controlled by mechanical stretching for the precise fabrication and consistent performance of helical microswimmers. Xylem vessels of a wide variety of different plants have been evaluated for the consistency and reproducibility of their helical parameters. Sequential deposition of thin Ti and Ni layers directly on the spiral vessels, followed by dicing, leads to an extremely simple and cost-efficient mass-production of functional helical microswimmers. The resulting plant-based magnetic microswimmers display efficient propulsion, with a speed of over 250 μm/s, as well as powerful locomotion in biological media such as human serum. The influence of actuation frequencies on the swimming velocity is investigated. Such use of plant vessels results in significant savings in the processing costs and provides an extremely simple, cost-effective fabrication route for the large-scale production of helical magnetic swimmers.

Highly Efficient Light-Driven TiO2–Au Janus Micromotors

A highly efficient light-driven photocatalytic TiO2-Au Janus micromotor with wireless steering and velocity control is described. Unlike chemically propelled micromotors which commonly require the addition of surfactants or toxic chemical fuels, the fuel-free Janus micromotor (diameter ∼1.0 μm) can be powered in pure water under an extremely low ultraviolet light intensity (2.5 × 10(-3) W/cm(2)), and with 40 × 10(-3) W/cm(2), they can reach a high speed of 25 body length/s, which is comparable to common Pt-based chemically induced self-electrophoretic Janus micromotors. The photocatalytic propulsion can be switched on and off by incident light modulation. In addition, the speed of the photocatalytic TiO2-Au Janus micromotor can be accelerated by increasing the light intensity or by adding low concentrations of chemical fuel H2O2 (i.e., 0.1%). The attractive fuel-free propulsion performance, fast movement triggering response, low light energy requirement, and precise motion control of the TiO2-Au Janus photocatalytic micromotor hold considerable promise for diverse practical applications.

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal

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.

Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy

Frozen in time The electrochemical processes occurring in a battery are highly dynamic. To understand the complexities of the charge and discharge cycles, you need to be able to watch the processes in situ or to freeze the battery rapidly for ex situ analysis. Li et al. applied cryo–electron microscopy techniques commonly used for studying biological samples to examine batteries. They identified the solid electrolyte interphase that forms, observed the interactions of Li with the interphase, and captured the formation of dendrites that can be detrimental to the lifetime of a battery. Science, this issue p. 506 Cryo–electron microscopy can preserve reactive metals and thus reveal the atomic structure of a lithium metal dendrite. Whereas standard transmission electron microscopy studies are unable to preserve the native state of chemically reactive and beam-sensitive battery materials after operation, such materials remain pristine at cryogenic conditions. It is then possible to atomically resolve individual lithium metal atoms and their interface with the solid electrolyte interphase (SEI). We observe that dendrites in carbonate-based electrolytes grow along the <111> (preferred), <110>, or <211> directions as faceted, single-crystalline nanowires. These growth directions can change at kinks with no observable crystallographic defect. Furthermore, we reveal distinct SEI nanostructures formed in different electrolytes.

Nanoscale perspective: Materials designs and understandings in lithium metal anodes

Li metal chemistry is a promising alternative with a much higher energy density than that of state-of-the-art Li-ion counterparts. However, significant challenges including safety issues and poor cyclability have severely impeded Li metal technology from becoming viable. In recent years, nanotechnologies have become increasingly important in materials design and fabrication for Li metal anodes, contributing to major progress in the field. In this review, we first introduce the main achievements in Li metal battery systems fulfilled by nanotechnologies, particularly regarding Li metal anode design and protection, ultrastrong separator engineering, safety monitoring, and smart functions. Next, we introduce recent studies on nanoscale Li nucleation/deposition. Finally, we discuss possible future research directions. We hope this review delivers an overall picture of the role of nanoscale approaches in the recent progress of Li metal battery technology and inspires more research in the future.

Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode

Selective atomic layer deposition of LiF on h-BN as an interfacial layer enables stable cycling of Li metal anodes. Defects are important features in two-dimensional (2D) materials that have a strong influence on their chemical and physical properties. Through the enhanced chemical reactivity at defect sites (point defects, line defects, etc.), one can selectively functionalize 2D materials via chemical reactions and thereby tune their physical properties. We demonstrate the selective atomic layer deposition of LiF on defect sites of h-BN prepared by chemical vapor deposition. The LiF deposits primarily on the line and point defects of h-BN, thereby creating seams that hold the h-BN crystallites together. The chemically and mechanically stable hybrid LiF/h-BN film successfully suppresses lithium dendrite formation during both the initial electrochemical deposition onto a copper foil and the subsequent cycling. The protected lithium electrodes exhibit good cycling behavior with more than 300 cycles at relatively high coulombic efficiency (>95%) in an additive-free carbonate electrolyte.

Robust Pinhole-free Li3N Solid Electrolyte Grown from Molten Lithium

Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li3N film directly bonded onto Li metal foil. The film consists of highly textured large Li3N grains (tens of μm) with (001) crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10–4 S cm–1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li3N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li4Ti5O12 cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis.

Strong texturing of lithium metal in batteries

Significance This work represents a first attempt to study the crystallographic texture of Li metal in batteries. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposition is primarily dependent on the type of additive or cross-over molecule from the cathode side. We find that reversibility of Li, which is phenomenologically influenced by morphology, is fundamentally driven by the texture (crystallographic orientation). Additives in electrolytes and the cross-over molecules from the cathode play crucial roles on the crystallographic texture because they hinder the cathodic process and selectively adsorb/react on different crystal planes. Additives with favorable adsorption and reusability will generate controllable texture, resulting in more uniform morphology and better cycling reversibility. Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type of additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. This understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.

Revealing Nanoscale Passivation and Corrosion Mechanisms of Reactive Battery Materials in Gas Environments

Lithium (Li) metal is a high-capacity anode material (3860 mAh g-1) that can enable high-energy batteries for electric vehicles and grid-storage applications. However, Li metal is highly reactive and repeatedly consumed when exposed to liquid electrolyte (during battery operation) or the ambient environment (throughout battery manufacturing). Studying these corrosion reactions on the nanoscale is especially difficult due to the high chemical reactivity of both Li metal and its surface corrosion films. Here, we directly generate pure Li metal inside an environmental transmission electron microscope (TEM), revealing the nanoscale passivation and corrosion process of Li metal in oxygen (O2), nitrogen (N2), and water vapor (H2O). We find that while dry O2 and N2 (99.9999 vol %) form uniform passivation layers on Li, trace water vapor (∼1 mol %) disrupts this passivation and forms a porous film on Li metal that allows gas to penetrate and continuously react with Li. To exploit the self-passivating behavior of Li in dry conditions, we introduce a simple dry-N2 pretreatment of Li metal to form a protective layer of Li nitride prior to battery assembly. The fast ionic conductivity and stable interface of Li nitride results in improved battery performance with dendrite-free cycling and low voltage hysteresis. Our work reveals the detailed process of Li metal passivation/corrosion and demonstrates how this mechanistic insight can guide engineering solutions for Li metal batteries.