Electrotunable liquid sulfur microdroplets.

Manipulating liquids with tunable shape and optical functionalities in real time is important for electroactive flow devices and optoelectronic devices, but remains a great challenge. Here, we demonstrate electrotunable liquid sulfur microdroplets in an electrochemical cell. We observe electrowetting and merging of sulfur droplets under different potentiostatic conditions, and successfully control these processes via selective design of sulfiphilic/sulfiphobic substrates. Moreover, we employ the electrowetting phenomena to create a microlens based on the liquid sulfur microdroplets and tune its characteristics in real time through changing the shape of the liquid microdroplets in a fast, repeatable, and controlled manner. These studies demonstrate a powerful in situ optical battery platform for unraveling the complex reaction mechanism of sulfur chemistries and for exploring the rich material properties of the liquid sulfur, which shed light on the applications of liquid sulfur droplets in devices such as microlenses, and potentially other electrotunable and optoelectronic devices.

Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries.

The urgent need for safer batteries is leading research to all-solid-state lithium-based cells. To achieve energy density comparable to liquid electrolyte-based cells, ultrathin and lightweight solid electrolytes with high ionic conductivity are desired. However, solid electrolytes with comparable thicknesses to commercial polymer electrolyte separators (~10 µm) used in liquid electrolytes remain challenging to make because of the increased risk of short-circuiting the battery. Here, we report on a polymer-polymer solid-state electrolyte design, demonstrated with an 8.6-µm-thick nanoporous polyimide (PI) film filled with polyethylene oxide/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI) that can be used as a safe solid polymer electrolyte. The PI film is nonflammable and mechanically strong, preventing batteries from short-circuiting even after more than 1,000 h of cycling, and the vertical channels enhance the ionic conductivity (2.3 × 10-4 S cm-1 at 30 °C) of the infused polymer electrolyte. All-solid-state lithium-ion batteries fabricated with PI/PEO/LiTFSI solid electrolyte show good cycling performance (200 cycles at C/2 rate) at 60 °C and withstand abuse tests such as bending, cutting and nail penetration.

Precise Perforation and Scalable Production of Si Particles from Low-Grade Sources for High-Performance Lithium Ion Battery Anodes.

Alloy anodes, particularly silicon, have been intensively pursued as one of the most promising anode materials for the next generation lithium-ion battery primarily because of high specific capacity (>4000 mAh/g) and elemental abundance. In the past decade, various nanostructures with porosity or void space designs have been demonstrated to be effective to accommodate large volume expansion (∼300%) and to provide stable solid electrolyte interphase (SEI) during electrochemical cycling. However, how to produce these building blocks with precise morphology control at large scale and low cost remains a challenge. In addition, most of nanostructured silicon suffers from poor Coulombic efficiency due to a large surface area and Li ion trapping at the surface coating. Here we demonstrate a unique nanoperforation process, combining modified ball milling, annealing, and acid treating, to produce porous Si with precise and continuous porosity control (from 17% to 70%), directly from low cost metallurgical silicon source (99% purity, ∼ $1/kg). The produced porous Si coated with graphene by simple ball milling can deliver a reversible specific capacity of 1250 mAh/g over 1000 cycles at the rate of 1C, with Coulombic efficiency of first cycle over 89.5%. The porous networks also provide efficient ion and electron pathways and therefore enable excellent rate performance of 880 mAh/g at the rate of 5C. Being able to produce particles with precise porosity control through scalable processes from low-grade materials, it is expected that this nanoperforation may play a role in the next generation lithium ion battery anodes, as well as many other potential applications such as optoelectronics and thermoelectrics.

Simultaneous Purification and Perforation of Low-Grade Si Sources for Lithium-Ion Battery Anode.

Silicon is regarded as one of the most promising candidates for lithium-ion battery anodes because of its abundance and high theoretical capacity. Various silicon nanostructures have been heavily investigated to improve electrochemical performance by addressing issues related to structure fracture and unstable solid-electrolyte interphase (SEI). However, to further enable widespread applications, scalable and cost-effective processes need to be developed to produce these nanostructures at large quantity with finely controlled structures and morphologies. In this study, we develop a scalable and low cost process to produce porous silicon directly from low grade silicon through ball-milling and modified metal-assisted chemical etching. The morphology of porous silicon can be drastically changed from porous-network to nanowire-array by adjusting the component in reaction solutions. Meanwhile, this perforation process can also effectively remove the impurities and, therefore, increase Si purity (up to 99.4%) significantly from low-grade and low-cost ferrosilicon (purity of 83.4%) sources. The electrochemical examinations indicate that these porous silicon structures with carbon treatment can deliver a stable capacity of 1287 mAh g(-1) over 100 cycles at a current density of 2 A g(-1). This type of purified porous silicon with finely controlled morphology, produced by a scalable and cost-effective fabrication process, can also serve as promising candidates for many other energy applications, such as thermoelectrics and solar energy conversion devices.

Nanopurification of silicon from 84% to 99.999% purity with a simple and scalable process.

Silicon, with its great abundance and mature infrastructure, is a foundational material for a range of applications, such as electronics, sensors, solar cells, batteries, and thermoelectrics. These applications rely on the purification of Si to different levels. Recently, it has been shown that nanosized silicon can offer additional advantages, such as enhanced mechanical properties, significant absorption enhancement, and reduced thermal conductivity. However, current processes to produce and purify Si are complex, expensive, and energy-intensive. Here, we show a nanopurification process, which involves only simple and scalable ball milling and acid etching, to increase Si purity drastically [up to 99.999% (wt %)] directly from low-grade and low-cost ferrosilicon [84% (wt %) Si; ∼$1/kg]. It is found that the impurity-rich regions are mechanically weak as breaking points during ball milling and thus, exposed on the surface, and they can be conveniently and effectively removed by chemical etching. We discovered that the purity goes up with the size of Si particles going down, resulting in high purity at the sub-100-nm scale. The produced Si nanoparticles with high purity and small size exhibit high performance as Li ion battery anodes, with high reversible capacity (1,755 mAh g(-1)) and long cycle life (73% capacity retention over 500 cycles). This nanopurification process provides a complimentary route to produce Si, with finely controlled size and purity, in a diverse set of applications.

Scalable Production of Si Nanoparticles Directly from Low Grade Sources for Lithium-Ion Battery Anode.

Silicon, one of the most promising candidates as lithium-ion battery anode, has attracted much attention due to its high theoretical capacity, abundant existence, and mature infrastructure. Recently, Si nanostructures-based lithium-ion battery anode, with sophisticated structure designs and process development, has made significant progress. However, low cost and scalable processes to produce these Si nanostructures remained as a challenge, which limits the widespread applications. Herein, we demonstrate that Si nanoparticles with controlled size can be massively produced directly from low grade Si sources through a scalable high energy mechanical milling process. In addition, we systematically studied Si nanoparticles produced from two major low grade Si sources, metallurgical silicon (∼99 wt % Si, $1/kg) and ferrosilicon (∼83 wt % Si, $0.6/kg). It is found that nanoparticles produced from ferrosilicon sources contain FeSi2, which can serve as a buffer layer to alleviate the mechanical fractures of volume expansion, whereas nanoparticles from metallurgical Si sources have higher capacity and better kinetic properties because of higher purity and better electronic transport properties. Ferrosilicon nanoparticles and metallurgical Si nanoparticles demonstrate over 100 stable deep cycling after carbon coating with the reversible capacities of 1360 mAh g(-1) and 1205 mAh g(-1), respectively. Therefore, our approach provides a new strategy for cost-effective, energy-efficient, large scale synthesis of functional Si electrode materials.