Zhenda Lu

Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode.

Stable cycling of lithium metal anode is challenging due to the dendritic lithium formation and high chemical reactivity of lithium with electrolyte and nearly all the materials. Here, we demonstrate a promising novel electrode design by growing two-dimensional (2D) atomic crystal layers including hexagonal boron nitride (h-BN) and graphene directly on Cu metal current collectors. Lithium ions were able to penetrate through the point and line defects of the 2D layers during the electrochemical deposition, leading to sandwiched lithium metal between ultrathin 2D layers and Cu. The 2D layers afford an excellent interfacial protection of Li metal due to their remarkable chemical stability as well as mechanical strength and flexibility, resulting from the strong intralayer bonds and ultrathin thickness. Smooth Li metal deposition without dendritic and mossy Li formation was realized. We showed stable cycling over 50 cycles with Coulombic efficiency ∼97% in organic carbonate electrolyte with current density and areal capacity up to the practical value of 2.0 mA/cm(2)and 5.0 mAh/cm(2), respectively, which is a significant improvement over the unprotected electrodes in the same electrolyte.

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating

Significance This research paper presents a novel strategy for the fabrication of metal–scaffold composite materials. Particularly, molten lithium metal is infused into a surface-modified three-dimensional matrix with a “lithiophilic” coating. The resulting lithium–scaffold composite was used as battery anodes and exhibited superior performance compared with bare lithium metal anodes. Whereas the emphasis of this study is on lithium anodes, our present work opens up a direction for realization of other metal-anode–based systems. We believe the present work will contribute significantly to the energy-related field and also inspire research in other areas. Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium–scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with “lithiophilic” coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm2 over 80 cycles.

Nonfilling Carbon Coating of Porous Silicon Micrometer-Sized Particles for High-Performance Lithium Battery Anodes

Silicon is widely recognized as one of the most promising anode materials for lithium-ion batteries due to its 10 times higher specific capacity than graphite. Unfortunately, the large volume change of Si materials during their lithiation/delithiation process results in severe pulverization, loss of electrical contact, unstable solid-electrolyte interphase (SEI), and eventual capacity fading. Although there has been tremendous progress to overcome these issues through nanoscale materials design, improved volumetric capacity and reduced cost are still needed for practical application. To address these issues, we design a nonfilling carbon-coated porous silicon microparticle (nC-pSiMP). In this structure, porous silicon microparticles (pSiMPs) consist of many interconnected primary silicon nanoparticles; only the outer surface of the pSiMPs was coated with carbon, leaving the interior pore structures unfilled. Nonfilling carbon coating hinders electrolyte penetration into the nC-pSiMPs, minimizes the electrode-electrolyte contact area, and retains the internal pore space for Si expansion. SEI formation is mostly limited to the outside of the microparticles. As a result, the composite structure demonstrates excellent cycling stability with high reversible specific capacity (∼1500 mAh g(-1), 1000 cycles) at the rate of C/4. The nC-pSiMPs contain accurate void space to accommodate Si expansion while not losing packing density, which allows for a high volumetric capacity (∼1000 mAh cm(-3)). The areal capacity can reach over 3 mAh cm(-2) with the mass loading 2.01 mg cm(-2). Moreover, the production of nC-pSiMP is simple and scalable using a low-cost silicon monoxide microparticle starting material.

A high tap density secondary silicon particle anode fabricated by scalable mechanical pressing for lithium-ion batteries

Much progress has been made in developing high capacity lithium ion battery electrode materials such as silicon anodes. With the powerful nanomaterial design approach, cycle life of silicon anodes has been increased significantly. However, nanomaterials have three major issues to be addressed, including severe side reactions due to a large surface area, low tap density and poor scalability. Nanostructured Si secondary clusters (nano-Si SC) are promising for reducing side reactions and increasing tap density, yet the scalability and tap density could still be further improved. Here, we propose a mechanical approach for SC fabrication to address all the problems. With the mechanical approach, >20 g of nano-Si SC per batch was produced even at our university lab scale, with >95% yield. Moreover, much denser packing of nanostructures can be achieved (1.38 g cm−3, pellet form), which gives much higher tap density (0.91 g cm−3, powder form) and better electrical contact. Accordingly, over 95% of initial capacity is retained after 1400 cycles at 1C, with an average specific capacity of ∼1250 mA h g−1. Stable cycling with >2 mg cm−2 of areal mass loading (∼3.5 mA h cm−2) is obtained. After uniformly integrating carbon nanotubes (CNTs) into SCs, intracluster electrical conductivity is further improved. As a result, notably enhanced rate capability is attained, with a high reversible specific capacity of ∼1140 mA h g−1 and ∼880 mA h g−1 at 2C and 4C, respectively.

Crab Shells as Sustainable Templates from Nature for Nanostructured Battery Electrodes

Rational nanostructure design has been a promising route to address critical materials issues for enabling next-generation high capacity lithium ion batteries for portable electronics, vehicle electrification, and grid-scale storage. However, synthesis of functional nanostructures often involves expensive starting materials and elaborate processing, both of which present a challenge for successful implementation in low-cost applications. In seeking a sustainable and cost-effective route to prepare nanostructured battery electrode materials, we are inspired by the diversity of natural materials. Here, we show that crab shells with the unique Bouligand structure consisting of highly mineralized chitin-protein fibers can be used as biotemplates to fabricate hollow carbon nanofibers; these fibers can then be used to encapsulate sulfur and silicon to form cathodes and anodes for Li-ion batteries. The resulting nanostructured electrodes show high specific capacities (1230 mAh/g for sulfur and 3060 mAh/g for silicon) and excellent cycling performance (up to 200 cycles with 60% and 95% capacity retention, respectively). Since crab shells are readily available due to the 0.5 million tons produced annually as a byproduct of crab consumption, their use as a sustainable and low-cost nanotemplate represents an exciting direction for nanostructured battery materials.

Artificial Solid Electrolyte Interphase-Protected LixSi Nanoparticles: An Efficient and Stable Prelithiation Reagent for Lithium-Ion Batteries.

Prelithiation is an important strategy to compensate for lithium loss in lithium-ion batteries, particularly during the formation of the solid electrolyte interphase (SEI) from reduced electrolytes in the first charging cycle. We recently demonstrated that LixSi nanoparticles (NPs) synthesized by thermal alloying can serve as a high-capacity prelithiation reagent, although their chemical stability in the battery processing environment remained to be improved. Here we successfully developed a surface modification method to enhance the stability of LixSi NPs by exploiting the reduction of 1-fluorodecane on the LixSi surface to form a continuous and dense coating through a reaction process similar to SEI formation. The coating, consisting of LiF and lithium alkyl carbonate with long hydrophobic carbon chains, serves as an effective passivation layer in the ambient environment. Remarkably, artificial-SEI-protected LixSi NPs show a high prelithiation capacity of 2100 mA h g(-1) with negligible capacity decay in dry air after 5 days and maintain a high capacity of 1600 mA h g(-1) in humid air (∼10% relative humidity). Silicon, tin, and graphite were successfully prelithiated with these NPs to eliminate the irreversible first-cycle capacity loss. The use of prelithiation reagents offers a new approach to realize next-generation high-energy-density lithium-ion batteries.

Dry-air-stable lithium silicide–lithium oxide core–shell nanoparticles as high-capacity prelithiation reagents

Rapid progress has been made in realizing battery electrode materials with high capacity and long-term cyclability in the past decade. However, low first-cycle Coulombic efficiency as a result of the formation of a solid electrolyte interphase and Li trapping at the anodes, remains unresolved. Here we report LixSi-Li2O core-shell nanoparticles as an excellent prelithiation reagent with high specific capacity to compensate the first-cycle capacity loss. These nanoparticles are produced via a one-step thermal alloying process. LixSi-Li2O core-shell nanoparticles are processible in a slurry and exhibit high capacity under dry-air conditions with the protection of a Li2O passivation shell, indicating that these nanoparticles are potentially compatible with industrial battery fabrication processes. Both Si and graphite anodes are successfully prelithiated with these nanoparticles to achieve high first-cycle Coulombic efficiencies of 94% to >100%. The LixSi-Li2O core-shell nanoparticles enable the practical implementation of high-performance electrode materials in lithium-ion batteries.

Direct Conversion of Perovskite Thin Films into Nanowires with Kinetic Control for Flexible Optoelectronic Devices

With significant progress in the past decade, semiconductor nanowires have demonstrated unique features compared to their thin film counterparts, such as enhanced light absorption, mechanical integrity and reduced therma conductivity, etc. However, technologies of semiconductor thin film still serve as foundations of several major industries, such as electronics, displays, energy, etc. A direct path to convert thin film to nanowires can build a bridge between these two and therefore facilitate the large-scale applications of nanowires. Here, we demonstrate that methylammonium lead iodide (CH3NH3PbI3) nanowires can be synthesized directly from perovskite film by a scalable conversion process. In addition, with fine kinetic control, morphologies, and diameters of these nanowires can be well-controlled. Based on these perovskite nanowires with excellent optical trapping and mechanical properties, flexible photodetectors with good sensitivity are demonstrated.

In situ observation of divergent phase transformations in individual sulfide nanocrystals.

Inorganic nanocrystals have attracted widespread attention both for their size-dependent properties and for their potential use as building blocks in an array of applications. A complete understanding of chemical transformations in nanocrystals is important for controlling structure, composition, and electronic properties. Here, we utilize in situ high-resolution transmission electron microscopy to study structural and morphological transformations in individual sulfide nanocrystals (copper sulfide, iron sulfide, and cobalt sulfide) as they react with lithium. The experiments reveal the influence of structure and composition on the transformation pathway (conversion versus displacement reactions), and they provide a high-resolution view of the unique displacement reaction mechanism in copper sulfide in which copper metal is extruded from the crystal. The structural similarity between the initial and final phases, as well as the mobility of ions within the crystal, are seen to exert a controlling influence on the reaction pathway.

Core–Shell Nanoparticle Coating as an Interfacial Layer for Dendrite-Free Lithium Metal Anodes

Lithium metal based batteries represent a major challenge and opportunity in enabling a variety of devices requiring high-energy-density storage. However, dendritic lithium growth has limited the practical application of lithium metal anodes. Here we report a nanoporous, flexible and electrochemically stable coating of silica@poly(methyl methacrylate) (SiO2@PMMA) core–shell nanospheres as an interfacial layer on lithium metal anode. This interfacial layer is capable of inhibiting Li dendrite growth while sustaining ionic flux through it, which is attributed to the nanoscaled pores formed among the nanospheres. Enhanced Coulombic efficiencies during lithium charge/discharge cycles have been achieved at various current densities and areal capacities.