Judy J. Cha

Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries

Sulphur is an attractive cathode material with a high specific capacity of 1,673 mAh g(-1), but its rapid capacity decay owing to polysulphide dissolution presents a significant technical challenge. Despite much efforts in encapsulating sulphur particles with conducting materials to limit polysulphide dissolution, relatively little emphasis has been placed on dealing with the volumetric expansion of sulphur during lithiation, which will lead to cracking and fracture of the protective shell. Here, we demonstrate the design of a sulphur-TiO(2) yolk-shell nanoarchitecture with internal void space to accommodate the volume expansion of sulphur, resulting in an intact TiO(2) shell to minimize polysulphide dissolution. An initial specific capacity of 1,030 mAh g(-1) at 0.5 C and Coulombic efficiency of 98.4% over 1,000 cycles are achieved. Most importantly, the capacity decay after 1,000 cycles is as small as 0.033% per cycle, which represents the best performance for long-cycle lithium-sulphur batteries so far.

Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers

Layered materials consist of molecular layers stacked together by weak interlayer interactions. They often crystallize to form atomically smooth thin films, nanotubes, and platelet or fullerene-like nanoparticles due to the anisotropic bonding. Structures that predominately expose edges of the layers exhibit high surface energy and are often considered unstable. In this communication, we present a synthesis process to grow MoS2 and MoSe2 thin films with vertically aligned layers, thereby maximally exposing the edges on the film surface. Such edge-terminated films are metastable structures of MoS2 and MoSe2, which may find applications in diverse catalytic reactions. We have confirmed their catalytic activity in a hydrogen evolution reaction (HER), in which the exchange current density correlates directly with the density of the exposed edge sites.

Hollow carbon nanofiber-encapsulated sulfur cathodes for high specific capacity rechargeable lithium batteries.

Sulfur has a high specific capacity of 1673 mAh/g as lithium battery cathodes, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a hollow carbon nanofiber-encapsulated sulfur cathode for effective trapping of polysulfides and demonstrate experimentally high specific capacity and excellent electrochemical cycling of the cells. The hollow carbon nanofiber arrays were fabricated using anodic aluminum oxide (AAO) templates, through thermal carbonization of polystyrene. The AAO template also facilitates sulfur infusion into the hollow fibers and prevents sulfur from coating onto the exterior carbon wall. The high aspect ratio of the carbon nanofibers provides an ideal structure for trapping polysulfides, and the thin carbon wall allows rapid transport of lithium ions. The small dimension of these nanofibers provides a large surface area per unit mass for Li(2)S deposition during cycling and reduces pulverization of electrode materials due to volumetric expansion. A high specific capacity of about 730 mAh/g was observed at C/5 rate after 150 cycles of charge/discharge. The introduction of LiNO(3) additive to the electrolyte was shown to improve the Coulombic efficiency to over 99% at C/5. The results show that the hollow carbon nanofiber-encapsulated sulfur structure could be a promising cathode design for rechargeable Li/S batteries with high specific energy.

Improving the performance of lithium-sulfur batteries by conductive polymer coating.

Rechargeable lithium–sulfur (Li–S) batteries hold great potential for next-generation high-performance energy storage systems because of their high theoretical specific energy, low materials cost, and environmental safety. One of the major obstacles for its commercialization is the rapid capacity fading due to polysulfide dissolution and uncontrolled redeposition. Various porous carbon structures have been used to improve the performance of Li–S batteries, as polysulfides could be trapped inside the carbon matrix. However, polysulfides still diffuse out for a prolonged time if there is no effective capping layer surrounding the carbon/sulfur particles. Here we explore the application of conducting polymer to minimize the diffusion of polysulfides out of the mesoporous carbon matrix by coating poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) onto mesoporous carbon/sulfur particles. After surface coating, coulomb efficiency of the sulfur electrode was improved from 93% to 97%, and capaci...

Electrospun Metal Nanofiber Webs as High-Performance Transparent Electrode

Transparent electrodes, indespensible in displays and solar cells, are currently dominated by indium tin oxide (ITO) films although the high price of indium, brittleness of films, and high vacuum deposition are limiting their applications. Recently, solution-processed networks of nanostructures such as carbon nanotubes (CNTs), graphene, and silver nanowires have attracted great attention as replacements. A low junction resistance between nanostructures is important for decreasing the sheet resistance. However, the junction resistances between CNTs and boundry resistances between graphene nanostructures are too high. The aspect ratios of silver nanowires are limited to ∼100, and silver is relatively expensive. Here, we show high-performance transparent electrodes with copper nanofiber networks by a low-cost and scalable electrospinning process. Copper nanofibers have ultrahigh aspect ratios of up to 100000 and fused crossing points with ultralow junction resistances, which result in high transmitance at low sheet resistance, e.g., 90% at 50 Ω/sq. The copper nanofiber networks also show great flexibility and stretchabilty. Organic solar cells using copper nanowire networks as transparent electrodes have a power efficiency of 3.0%, comparable to devices made with ITO electrodes.

New Nanostructured Li2S/Silicon Rechargeable Battery with High Specific Energy

Rechargeable lithium ion batteries are important energy storage devices; however, the specific energy of existing lithium ion batteries is still insufficient for many applications due to the limited specific charge capacity of the electrode materials. The recent development of sulfur/mesoporous carbon nanocomposite cathodes represents a particularly exciting advance, but in full battery cells, sulfur-based cathodes have to be paired with metallic lithium anodes as the lithium source, which can result in serious safety issues. Here we report a novel lithium metal-free battery consisting of a Li(2)S/mesoporous carbon composite cathode and a silicon nanowire anode. This new battery yields a theoretical specific energy of 1550 Wh kg(-1), which is four times that of the theoretical specific energy of existing lithium-ion batteries based on LiCoO(2) cathodes and graphite anodes (approximately 410 Wh kg(-1)). The nanostructured design of both electrodes assists in overcoming the issues associated with using sulfur compounds and silicon in lithium-ion batteries, including poor electrical conductivity, significant structural changes, and volume expansion. We have experimentally realized an initial discharge specific energy of 630 Wh kg(-1) based on the mass of the active electrode materials.

First-row transition metal dichalcogenide catalysts for hydrogen evolution reaction

A group of first-row transition metal dichalcogenides (ME2, M = Fe, Co, Ni; E = S, Se) are introduced as non-precious HER catalysts in an acidic electrolyte. They exhibit excellent catalytic activity especially in their nanoparticle form. These compounds expand and enrich the family of high performance HER catalysts.

Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries

Tremendous effort has been put into developing viable lithium sulfur batteries, due to their high specific energy and relatively low cost. Despite recent progress in addressing the various problems of sulfur cathodes, lithium sulfur batteries still exhibit significant capacity decay over cycling. Herein, we identify a new capacity fading mechanism of the sulfur cathodes, relating to Li(x)S detachment from the carbon surface during the discharge process. This observation is confirmed by ex-situ transmission electron microscopy study and first-principles calculations. We demonstrate that this capacity fading mechanism can be overcome by introducing amphiphilic polymers to modify the carbon surface, rendering strong interactions between the nonpolar carbon and the polar Li(x)S clusters. The modified sulfur cathode show excellent cycling performance with specific capacity close to 1180 mAh/g at C/5 current rate. Capacity retention of 80% is achieved over 300 cycles at C/2.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

Significance The electronic structures of two-dimensional materials can be tuned for a variety of applications by guest species intercalation into the van der Waals gaps. Using Li electrochemical intercalated MoS2 as an example here, we correlate the continuously tuned electronic structure of lithiated MoS2 with the corresponding enhanced hydrogen evolution reaction activity, and thus construct the electronic structure–catalytic activity relationship. This work offers a unique thinking of tuning the electronic structures of layered materials by guest species intercalation for optimizing different kinds of catalysis on the basis of the strong correlation between the electronic structures and catalytic activities of the catalysts. The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity.

MoSe2 and WSe2 nanofilms with vertically aligned molecular layers on curved and rough surfaces.

Two-dimensional (2D) layered materials exhibit high anisotropy in materials properties due to the large difference of intra- and interlayer bonding. This presents opportunities to engineer materials whose properties strongly depend on the orientation of the layers relative to the substrate. Here, using a similar growth process reported in our previous study of MoS2 and MoSe2 films whose layers were oriented vertically on flat substrates, we demonstrate that the vertical layer orientation can be realized on curved and rough surfaces such as nanowires (NWs) and microfibers. Such structures can increase the surface area while maintaining the perpendicular orientation of the layers, which may be useful in enhancing various catalytic activities. We show vertically aligned MoSe2 and WSe2 nanofilms on Si NWs and carbon fiber paper. We find that MoSe2 and WSe2 nanofilms on carbon fiber paper are highly efficient electrocatalysts for hydrogen evolution reaction (HER) compared to flat substrates. Both materials exhibit extremely high stability in acidic solution as the HER catalytic activity shows no degradation after 15 000 continuous potential cycles. The HER activity of MoSe2 is further improved by Ni doping.