Liangbing Hu

Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control

Although the performance of lithium ion-batteries continues to improve, their energy density and cycle life remain insufficient for applications in consumer electronics, transport and large-scale renewable energy storage. Silicon has a large charge storage capacity and this makes it an attractive anode material, but pulverization during cycling and an unstable solid-electrolyte interphase has limited the cycle life of silicon anodes to hundreds of cycles. Here, we show that anodes consisting of an active silicon nanotube surrounded by an ion-permeable silicon oxide shell can cycle over 6,000 times in half cells while retaining more than 85% of their initial capacity. The outer surface of the silicon nanotube is prevented from expansion by the oxide shell, and the expanding inner surface is not exposed to the electrolyte, resulting in a stable solid-electrolyte interphase. Batteries containing these double-walled silicon nanotube anodes exhibit charge capacities approximately eight times larger than conventional carbon anodes and charging rates of up to 20C (a rate of 1C corresponds to complete charge or discharge in one hour).

Solution-Processed Graphene/MnO2 Nanostructured Textiles for High-Performance Electrochemical Capacitors

Large scale energy storage system with low cost, high power, and long cycle life is crucial for addressing the energy problem when connected with renewable energy production. To realize grid-scale applications of the energy storage devices, there remain several key issues including the development of low-cost, high-performance materials that are environmentally friendly and compatible with low-temperature and large-scale processing. In this report, we demonstrate that solution-exfoliated graphene nanosheets (∼5 nm thickness) can be conformably coated from solution on three-dimensional, porous textiles support structures for high loading of active electrode materials and to facilitate the access of electrolytes to those materials. With further controlled electrodeposition of pseudocapacitive MnO(2) nanomaterials, the hybrid graphene/MnO(2)-based textile yields high-capacitance performance with specific capacitance up to 315 F/g achieved. Moreover, we have successfully fabricated asymmetric electrochemical capacitors with graphene/MnO(2)-textile as the positive electrode and single-walled carbon nanotubes (SWNTs)-textile as the negative electrode in an aqueous Na(2)SO(4) electrolyte solution. These devices exhibit promising characteristics with a maximum power density of 110 kW/kg, an energy density of 12.5 Wh/kg, and excellent cycling performance of ∼95% capacitance retention over 5000 cycles. Such low-cost, high-performance energy textiles based on solution-processed graphene/MnO(2) hierarchical nanostructures offer great promise in large-scale energy storage device applications.

Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life.

Silicon is a promising candidate for the anode material in lithium-ion batteries due to its high theoretical specific capacity. However, volume changes during cycling cause pulverization and capacity fade, and improving cycle life is a major research challenge. Here, we report a novel interconnected Si hollow nanosphere electrode that is capable of accommodating large volume changes without pulverization during cycling. We achieved the high initial discharge capacity of 2725 mAh g(-1) with less than 8% capacity degradation every hundred cycles for 700 total cycles. Si hollow sphere electrodes also show a Coulombic efficiency of 99.5% in later cycles. Superior rate capability is demonstrated and attributed to fast lithium diffusion in the interconnected Si hollow structure.

A transparent electrode based on a metal nanotrough network

Transparent conducting electrodes are essential components for numerous flexible optoelectronic devices, including touch screens and interactive electronics. Thin films of indium tin oxide-the prototypical transparent electrode material-demonstrate excellent electronic performances, but film brittleness, low infrared transmittance and low abundance limit suitability for certain industrial applications. Alternatives to indium tin oxide have recently been reported and include conducting polymers, carbon nanotubes and graphene. However, although flexibility is greatly improved, the optoelectronic performance of these carbon-based materials is limited by low conductivity. Other examples include metal nanowire-based electrodes, which can achieve sheet resistances of less than 10Ω □(-1) at 90% transmission because of the high conductivity of the metals. To achieve these performances, however, metal nanowires must be defect-free, have conductivities close to their values in bulk, be as long as possible to minimize the number of wire-to-wire junctions, and exhibit small junction resistance. Here, we present a facile fabrication process that allows us to satisfy all these requirements and fabricate a new kind of transparent conducting electrode that exhibits both superior optoelectronic performances (sheet resistance of ~2Ω □(-1) at 90% transmission) and remarkable mechanical flexibility under both stretching and bending stresses. The electrode is composed of a free-standing metallic nanotrough network and is produced with a process involving electrospinning and metal deposition. We demonstrate the practical suitability of our transparent conducting electrode by fabricating a flexible touch-screen device and a transparent conducting tape.

Electrospun Sb/C Fibers for a Stable and Fast Sodium-Ion Battery Anode

Sodium-ion batteries (SIBs) are considered a top alternative to lithium-ion batteries (LIBs) for large-scale renewable energy storage units due to their low cost and the abundance of sodium-bearing precursors in the earths mineral deposits. However, the development of anode materials for SIBs to date has been mainly limited to carbonaceous materials with minimal research devoted to high capacity alloy-based materials. In this study, an antimony (Sb)/carbon (C) electrode with ~30 nm Sb nanoparticles (NPs) uniformly encapsulated in interconnecting one-dimensional (1D) 400 nm carbon fibers (denoted as SbNP@C) was fabricated using a simple and scalable electrospinning method. This binder-free, current collector-free SbNP@C electrode demonstrated high capacity and stable long-term cycling performance at various current densities. The SbNP@C electrode showed an initial total capacity of 422 mAh/gelectrode and retained 350 mAh/gelectrode after 300 deep charge-discharge cycles under 100 mA/gSb. Moreover, because of the efficient 1D sodium-ion transport pathway and the highly conductive network of SbNP@C, the electrode preserved high overall capacities even when cycled at high currents, extending its usability to high power applications.

Tin Anode for Sodium-Ion Batteries Using Natural Wood Fiber as a Mechanical Buffer and Electrolyte Reservoir

Sodium (Na)-ion batteries offer an attractive option for low cost grid scale storage due to the abundance of Na. Tin (Sn) is touted as a high capacity anode for Na-ion batteries with a high theoretical capacity of 847 mAh/g, but it has several limitations such as large volume expansion with cycling, slow kinetics, and unstable solid electrolyte interphase (SEI) formation. In this article, we demonstrate that an anode consisting of a Sn thin film deposited on a hierarchical wood fiber substrate simultaneously addresses all the challenges associated with Sn anodes. The soft nature of wood fibers effectively releases the mechanical stresses associated with the sodiation process, and the mesoporous structure functions as an electrolyte reservoir that allows for ion transport through the outer and inner surface of the fiber. These properties are confirmed experimentally and computationally. A stable cycling performance of 400 cycles with an initial capacity of 339 mAh/g is demonstrated; a significant improvement over other reported Sn nanostructures. The soft and mesoporous wood fiber substrate can be utilized as a new platform for low cost Na-ion batteries.

Na-Ion Battery Anodes: Materials and Electrochemistry

The intermittent nature of renewable energy sources, such as solar and wind, calls for sustainable electrical energy storage (EES) technologies for stationary applications. Li will be simply too rare for Li-ion batteries (LIBs) to be used for large-scale storage purposes. In contrast, Na-ion batteries (NIBs) are highly promising to meet the demand of grid-level storage because Na is truly earth abundant and ubiquitous around the globe. Furthermore, NIBs share a similar rocking-chair operation mechanism with LIBs, which potentially provides high reversibility and long cycling life. It would be most efficient to transfer knowledge learned on LIBs during the last three decades to the development of NIBs. Following this logic, rapid progress has been made in NIB cathode materials, where layered metal oxides and polyanionic compounds exhibit encouraging results. On the anode side, pure graphite as the standard anode for LIBs can only form NaC64 in NIBs if solvent co-intercalation does not occur due to the unfavorable thermodynamics. In fact, it was the utilization of a carbon anode in LIBs that enabled the commercial successes. Anodes of metal-ion batteries determine key characteristics, such as safety and cycling life; thus, it is indispensable to identify suitable anode materials for NIBs. In this Account, we review recent development on anode materials for NIBs. Due to the limited space, we will mainly discuss carbon-based and alloy-based anodes and highlight progress made in our groups in this field. We first present what is known about the failure mechanism of graphite anode in NIBs. We then go on to discuss studies on hard carbon anodes, alloy-type anodes, and organic anodes. Especially, the multiple functions of natural cellulose that is used as a low-cost carbon precursor for mass production and as a soft substrate for tin anodes are highlighted. The strategies of minimizing the surface area of carbon anodes for improving the first-cycle Coulombic efficiency are also outlined, where graphene oxide was employed as dehydration agent and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was used to unzip wood fiber. Furthermore, surface modification by atomic layer deposition technology is introduced, where we discover that a thin layer of Al2O3 can function to encapsulate Sn nanoparticles, leading to a much enhanced cycling performance. We also highlight recent work about the phosphorene/graphene anode, which outperformed other anodes in terms of capacity. The aromatic organic anode is also studied as anode with very high initial sodiation capacity. Furthermore, electrochemical intercalation of Na ions into reduced graphene oxide is applied for fabricating transparent conductors, demonstrating the great feasibility of Na ion intercalation for optical applications.

Prelithiated Silicon Nanowires as an Anode for Lithium Ion Batteries

Silicon is one of the most promising anode materials for the next-generation high-energy lithium ion battery (LIB), while sulfur and some other lithium-free materials have recently shown high promise as cathode materials. To make a full battery out of them, either the cathode or the anode needs to be prelithiated. Here, we present a method for prelithiating a silicon nanowire (SiNW) anode by a facile self-discharge mechanism. Through a time dependence study, we found that 20 min of prelithiation loads ∼50% of the full capacity into the SiNWs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies show that the nanostructure of SiNWs is maintained after prelithiation. We constructed a full battery using our prelithiated SiNW anode with a sulfur cathode. Our work provides a protocol for pairing lithium-free electrodes to make the next-generation high-energy LIB.

Negating interfacial impedance in garnet-based solid-state Li metal batteries

Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic conductivity, approaching 1 mS cm-1, excellent environmental stability, and wide electrochemical stability window, from lithium metal to ∼6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid-solid interfacial impedance between the garnet electrolyte and electrode materials. In this work, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminium oxide (Al2O3) by atomic layer deposition. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) is the garnet composition of choice in this work due to its reduced sintering temperature and increased lithium ion conductivity. A significant decrease of interfacial impedance, from 1,710 Ω cm2 to 1 Ω cm2, was observed at room temperature, effectively negating the lithium metal/garnet interfacial impedance. Experimental and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. We also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chemistry.

Transparent paper: fabrications, properties, and device applications

Although paper electronics is a compelling concept, the large surface roughness and opaqueness of most paper substrates has hindered its development from a dormant idea to a thriving technology. A recent demonstration of transparent paper with nanoscale surface roughness has revived an interest in using renewable cellulose substrates for electronics and optoelectronics. In this short review, we will first summarize the recent progress of transparent paper electronics through structure engineering. We will also discuss the properties and functionalization of transparent paper, such as surface roughness, printability, thermal stability, etc. Finally, we will summarize the recent achievements on proof-of-concepts of transparent paper, which pave the way for next-generation green electronics fabricated with roll-to-roll printing methods. Advantages of transparent paper over traditional flexible plastic substrates and its challenges will also be discussed.