Hyejung Kim

MoS2 Nanoplates Consisting of Disordered Graphene-like Layers for High Rate Lithium Battery Anode Materials

MoS(2) nanoplates, consisting of disordered graphene-like layers, with a thickness of ∼30 nm were prepared by a simple, scalable, one-pot reaction using Mo(CO)(6) and S in an autoclave. The product has a interlayer distance of 0.69 nm, which is much larger than its bulk counterpart (0.62 nm). This expanded interlater distance and disordered graphene-like morphology led to an excellent rate capability even at a 50C (53.1 A/g) rate, showing a reversible capacity of 700 mAh/g. In addition, a full cell (LiCoO(2)/MoS(2)) test result also demonstrates excellent capacity retention up to 60 cycles.

A Critical Size of Silicon Nano-Anodes for Lithium Rechargeable Batteries

Due to the high theoretical capacity (ca. 4200 mAhg ) of Si when Li4.4Si is formed, it has been extensively investigated for use as a high-capacity anode material that can replace graphite, which is currently used (372 mAhg ). However, Si exhibits significant volume changes (> 360%) during Li alloying and dealloying. These changes cause cracking and crumbling of the electrode material and a consequent loss of electrical contact between individual particles and hence severe capacity drop. However, such mechanical strain induced by volume change can be reduced by employing smaller particles. To this end, synthetic methods such as spark ablation, aerogel techniques, and sputtering have been employed. Formation of crystalline Si nanoparticles requires higher temperatures due to the more covalent nature of these particles compared to Ge particles, and at low temperature amorphous phases become more common. The first commonly recognized successful production of Si nanoclusters was reported byHeath et al. They showed that Si nanocrystals capped with alkyl groups can be produced by reduction of SiCl4 and RSiCl3 (R=H, C8H17) according to the reaction SiCl4+RSiCl3+Na!Si+NaCl. This process was carried out at high temperature (385 8C) and high pressure (>100 atm) in a steel bomb fitted into a heating mantle. A process that utilizes SiCl4 reduction at room temperature under an inert atmosphere was initially reported by Kauzlarich et al. However, the drawback of their method was that the product obtained at room temperature was not fully crystallized and was severely capped with alkyl terminators. Moreover, an annealing process above 900 8C is required to obtain the crystalline phase. Similar solution syntheses have been reported at low or high temperature after reducing Si salts with LiAlH4 [13,14] or alkyl silanes. However, all of these methods produce a broad particle size distribution or involve aggregation of the nanoparticles. Furthermore, they all yield amounts of material too small for use in anode production for lithium secondary batteries. We now report a synthetic method using reverse micelles at high pressure and temperature in a bomb that produces Si nanoparticles (n-Si) with various particle sizes without aggregation and thus enables the optimal nanoparticle size for use in anode materials to be chosen. Figure 1 shows the XRD pattern and TEM images of n-Si prepared with trimethyloctadecylammonium bromide (OTAB) surfactant. The XRD pattern clearly shows forma-

Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst.

Electrocatalysts for oxygen reduction are a critical component that may dramatically enhance the performance of fuel cells and metal-air batteries, which may provide the power for future electric vehicles. Here we report a novel bio-inspired composite electrocatalyst, iron phthalocyanine with an axial ligand anchored on single-walled carbon nanotubes, demonstrating higher electrocatalytic activity for oxygen reduction than the state-of-the-art Pt/C catalyst as well as exceptional durability during cycling in alkaline media. Theoretical calculations suggest that the rehybridization of Fe 3d orbitals with the ligand orbitals coordinated from the axial direction results in a significant change in electronic and geometric structure, which greatly increases the rate of oxygen reduction reaction. Our results demonstrate a new strategy to rationally design inexpensive and durable electrochemical oxygen reduction catalysts for metal-air batteries and fuel cells.

Inhibition of human leukemia in an animal model with human antibodies directed against vascular endothelial growth factor receptor 2. Correlation between antibody affinity and biological activity

Vascular endothelial growth factor (VEGF) and its receptors (VEGFR) have been implicated in promoting solid tumor growth and metastasis via stimulating tumor-associated angiogenesis. We recently showed that certain ‘liquid’ tumors such as leukemia not only produce VEGF, but also express functional VEGFR, resulting in an autocrine loop for tumor growth and propagation. A chimeric anti-VEGFR2 (or kinase insert domain-containing receptor, KDR) antibody, IMC-1C11, was shown to be able to inhibit VEGF-induced proliferation of human leukemia cells in vitro, and to prolong survival of nonobese diabetic-severe combined immune deficient (NOD-SCID) mice inoculated with human leukemia cells. Here we produced two fully human anti-KDR antibodies (IgG1), IMC-2C6 and IMC-1121, from Fab fragments originally isolated from a large antibody phage display library. These antibodies bind specifically to KDR with high affinities: 50 and 200 pM for IMC-1121 and IMC-2C6, respectively, as compared to 270 pM for IMC-1C11. Like IMC-1C11, both human antibodies block VEGF/KDR interaction with an IC50 of approximately 1 nM, but IMC-1121 is a more potent inhibitor to VEGF-stimulated proliferation of human endothelial cells. These anti-KDR antibodies strongly inhibited VEGF-induced migration of human leukemia cells in vitro, and when administered in vivo, significantly prolonged survival of NOD-SCID mice inoculated with human leukemia cells. It is noteworthy that the mice treated with antibody of the highest affinity, IMC-1121, survived the longest period of time, followed by mice treated with IMC-2C6 and IMC-1C11. Taken together, our data suggest that anti-KDR antibodies may have broad applications in the treatment of both solid tumors and leukemia. It further underscores the efforts to identify antibodies of high affinity for enhanced antiangiogenic and antitumor activities.

Flexible high-energy Li-ion batteries with fast-charging capability

With the development of flexible mobile devices, flexible Li-ion batteries have naturally received much attention. Previously, all reported flexible components have had shortcomings related to power and energy performance. In this research, in order to overcome these problems while maintaining the flexibility, honeycomb-patterned Cu and Al materials were used as current collectors to achieve maximum adhesion in the electrodes. In addition, to increase the energy and power multishelled LiNi0.75Co0.11Mn0.14O2 particles consisting of nanoscale V2O5 and LixV2O5 coating layers and a LiδNi0.75-zCo0.11Mn0.14VzO2 doping layer were used as the cathode-anode composite (denoted as PNG-AES) consisting of amorphous Si nanoparticles (<20 nm) loaded on expanded graphite (10 wt %) and natural graphite (85 wt %). Li-ion cells with these three elements (cathode, anode, and current collector) exhibited excellent power and energy performance along with stable cycling stability up to 200 cycles in an in situ bending test.

The role of nanoscale-range vanadium treatment in LiNi0.8Co0.15Al0.05O2 cathode materials for Li-ion batteries at elevated temperatures

In order to overcome the inherent structural instability of bare LixNi0.8Co0.15Al0.05O2 (BNCA) containing large amounts of LiOH and Li2CO3 impurities at 60 and >200 °C, an effective nanoscale layer was generated by coating BNCA with an ammonium vanadate precursor, followed by annealing at 400 °C. This process forms a 17 nm thick surface layer containing V4+ ions in the transition metal 3b sites, thereby decreasing the thickness of the cation-mixing layer, which is the main factor responsible for destabilizing the surface structure. Such a coating also helps in substantially reducing the amount of surface impurities of LiOH, Li2CO3, and H2O by forming LiVO2, LiV2O5, VO2, and V2O5. Consequently, at 60 °C, vanadium-treated LiNi0.8Co0.15Al0.05O2 (VNCA) demonstrated excellent cyclability with a discharge capacity of 179 mA h g−1 after 200 cycles (after 17 days) between 3 and 4.3 V, corresponding to 90% capacity retention, which is 18% higher than the capacity retention measured for BNCA. More importantly, VNCA exhibits a significantly reduced heat generation and a higher onset temperature for exothermic reactions.

Lithium reaction mechanism and high rate capability of VS4–graphene nanocomposite as an anode material for lithium batteries

A graphene-attached VS4 composite prepared by a simple hydrothermal method is studied in terms of its lithium reaction mechanism and high rate capability. The nanocomposite exhibits a good cycling stability and an impressive high-rate capability for lithium storage, delivering a comparable capacity of 630 and 314 mA h g−1, even at high rates of 10 and 20 C (=10 and 20 A g−1, or 10 and 20 mA cm−2), respectively. In addition, full-cell (LiMn2O4/VS4–graphene) test results also exhibited a good capacity retention. The mechanism of Li storage is systematically studied and a conversion reaction with an irreversible phase change during the initial discharge–charge process is proposed.

Enhancing Interfacial Bonding between Anisotropically Oriented Grains using a Glue-Nanofiller for Advanced Li-ion Battery Cathode

Formation of a glue-nanofiller layer between grains, consisting of a middle-temperature spinel-like Lix CoO2 phase, reinforces the strength of the incoherent interfacial binding between anisotropically oriented grains by enhancing the face-to-face adhesion strength. The cathode treated with the glue-layer exhibits steady cycling performance at both room-temperature and 60 °C. These results represent a step forward in advanced lithium-ion batteries via simple cathode coating.

Li-Ion Battery Cathodes: Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode (Adv. Mater. 23/2016)

The formation of a spinel Lix CoO2 layer in a Ni-rich secondary particle for lithium-ion batteries is reported by S. K. Kwak, J. Cho, and co-workers on page 4705, who find that the spinel-like Lix CoO2 layer, between layered primary particles, can enhance the mechanical strength of secondary particles by enhancing the interfacial binding energy among the grains. Moreover, the layer can effectively protect the unstable surface of the primary particles and offers a fast electron-ion pathway, resulting in overall enhancements of stability and kinetics in battery performance.