Sandwich nanoarchitecture of LiV3O8/graphene multilayer nanomembranes via layer-by-layer self-assembly for long-cycle-life lithium-ion battery cathodes

A lack of suitable high-performance cathode materials has become the major barrier to their applications in future advanced communication equipment and electric vehicle power systems. In this paper, we have developed a layer-by-layer self-assembly approach for fabricating a novel sandwich nanoarchitecture of multilayered LiV₃O₈ nanoparticle/graphene nanosheet (M-nLVO/GN) hybrid electrodes for potential use in high performance lithium ion batteries by using a porous Ni foam as a substrate. The prepared sandwich nanoarchitecture of M-nLVO/GN hybrid electrodes exhibited high performance as a cathode material for lithium-ion batteries, such as high reversible specific capacity (235 mA h g^-1 at a current density of 0.3 A g^-1), high coulombic efficiency (over 98%), fast rate capability (up to a current density of 10 A g^-1), and superior capacity retention during cycling (90% capacity retention with a current density of 0.3 A g^-1 after 300 cycles). Very significantly, this novel insight into the design and synthesis of sandwich nanoarchitecture would extend their application to various electrochemical energy storage devices, such as fuel cells and supercapacitors.

A design strategy of large grain lithium-rich layered oxides for lithium-ion batteries cathode

Li-rich materials are considered the most promising for Li-ion battery cathodes, as high capacity can be achieved. However, poor cycling stability is a critical drawback that leads to poor capacity retention. Here a strategy is used to synthesize a large-grain lithium-rich layered oxides to overcome this difficulty without sacrificing rate capability. This material is designed with micron scale grain with a width of about 300 nm and length of 1-3 μm. This unique structure has a better ability to overcome stress-induced structural collapse caused by Li-ion insertion/extraction and reduce the dissolution of Mn ions, which enable a reversible and stable capacity. As a result, this cathode material delivered a highest discharge capacity of around 308 mAh g^-1 at a current density of 30 mA g^-1 with retention of 88.3% (according to the highest discharge capacity) after 100 cycles, 190 mAh g^-1 at a current density of 300 mA g^-1 and almost no capacity fading after 100 cycles. Therefore, Lithium-rich material of large-grain structure is a promising cathode candidate in Lithium-ion batteries with high capacity and high cycle stability for application. This strategy of large grain may furthermore open the door to synthesize the other complex architectures for various applications.

One-dimensional porous La0.5Sr0.5CoO2.91 nanotubes as a highly efficient electrocatalyst for rechargeable lithium-oxygen batteries

The electrochemical performance of one-dimensional porous La_0.5Sr_0.5CoO_2.91 nanotubes as a cathode catalyst for rechargeable nonaqueous lithium-oxygen (Li-O₂) batteries is reported here for the first time. In this study, one-dimensional porous La_0.5Sr_0.5CoO_2.91 nanotubes were prepared by a simple and efficient electrospinning technique. These materials displayed an initial discharge capacity of 7205 mAh g^-1 with a plateau at around 2.66 V at a current density of 100 mA g^-1. It was found that the La_0.5Sr_0.5CoO_2.91 nanotubes promoted both oxygen reduction and oxygen evolution reactions in alkaline media and a nonaqueous electrolyte, thereby improving the energy and coulombic efficiency of the Li-O₂ batteries. The cyclability was maintained for 85 cycles without any sharp decay under a limited discharge depth of 1000 mAh g^-1, suggesting that such a bifunctional electrocatalyst is a promising candidate for the oxygen electrode in Li-O₂ batteries.

In situ preparation of 3D graphene aerogels@hierarchical Fe3O4 nanoclusters as high rate and long cycle anode materials for lithium ion batteries

We describe a novel strategy for in situ fabrication of hierarchical Fe₃O₄ nanoclusters-GAs. Fe₃O₄ NCs-GAs deliver excellent rate capability (the reversible capacities obtained were 1442, 392 and 118 mA h g^-1 at 0.1C, 12C and 35C rates), and a high reversible capacity of 577 mA h g^-1 over 300 cycles at the current density of 5.2 A g^-1 (6C).

Surface modification of LiV3O8 nanosheets via layer-by-layer self-assembly for high-performance rechargeable lithium batteries

In this work, an economical route based on hydrothermal and layer-by-layer (LBL) self-assembly processes has been developed to synthesize unique Al ₂O₃-modified LiV₃O₈ nanosheets, comprising a core of LiV₃O₈ nanosheets and a thin Al ₂O₃ nanolayer. The thickness of the Al₂O ₃ nanolayer can be tuned by altering the LBL cycles. When evaluated for their lithium-storage properties, the 1 LBL Al₂O ₃-modified LiV₃O₈ nanosheets exhibit a high discharge capacity of 191 mA h g^-1 at 300 mA g^-1 (1C) over 200 cycles and excellent rate capability, demonstrating that enhanced physical and/or chemical properties can be achieved through proper surface modification. © 2014 Elsevier B.V. All rights reserved.

Facile synthesis of nanocrystalline LiFePO4/graphene composite as cathode material for high power lithium ion batteries

We describe a simple strategy, which is based on the idea of space confinement, for the synthesis of carbon coating on LiFePO₄ nanoparticles/graphene nanosheets composites in a water-in-oil emulsion system. The prepared composite displayed high performance as a cathode material for lithium-ion battery, such as high reversible lithium storage capacity (158 mA h g^-1 after 100 cycles), high coulombic efficiency (over 97%), excellent cycling stability and high rate capability (as high as 83 mA h g ^-1 at 60 C). Very significantly, the preparation method employed can be easily adapted and be extended as a general approach to sophisticated compositions and structures for the preparation of highly dispersed nanosized structure on graphene. 

Facile Synthesis of Anatase TiO2 Quantum-Dot/Graphene-Nanosheet Composites with Enhanced Electrochemical Performance for Lithium-Ion Batteries

A facile method to synthesize well-dispersed TiO₂ quantum dots on graphene nanosheets (TiO₂-QDs/GNs) in a water-in-oil (W/O) emulsion system is reported. The TiO₂/graphene composites display high performance as an anode material for lithium-ion batteries (LIBs), such as having high reversible lithium storage capacity, high Coulombic efficiency, excellent cycling stability, and high rate capability. The excellent electrochemical performance and special structure of the composites thus offer a way to prepare novel graphene-based electrode materials for high-energy-density and high-power LIBs. 

In situ synthesis of LiV3O8 nanorods on graphene as high rate-performance cathode materials for rechargeable lithium batteries

We developed a facile two-step hydrothermal procedure to prepare hybrid materials of LiV₃O₈ nanorods on graphene sheets. The special structure endows them with the high-rate transportation of electrolyte ions and electrons throughout the electrode matrix, resulting in remarkable electrochemical performance when they were used as cathodes in rechargeable lithium batteries. © 2013 The Royal Society of Chemistry.

An in situ ionic-liquid-assisted synthetic approach to iron fluoride/graphene hybrid nanostructures as superior cathode materials for lithium ion batteries

A tactful ionic-liquid (IL)-assisted approach to in situ synthesis of iron fluoride/graphene nanosheet (GNS) hybrid nanostructures is developed. To ensure uniform dispersion and tight anchoring of the iron fluoride on graphene, we employ an IL which serves not only as a green fluoride source for the crystallization of iron fluoride nanoparticles but also as a dispersant of GNSs. Owing to the electron transfer highways created between the nanoparticles and the GNSs, the iron fluoride/GNS hybrid cathodes exhibit a remarkable improvement in both capacity and rate performance (230 mAh g^-1 at 0.1 C and 74 mAh g^-1 at 40 C). The stable adhesion of iron fluoride nanoparticles on GNSs also introduces a significant improvement in long-term cyclic performance (115 mAh g^-1 after 250 cycles even at 10 C). The superior electrochemical performance of these iron fluoride/GNS hybrids as lithium ion battery cathodes is ascribed to the robust structure of the hybrid and the synergies between iron fluoride nanoparticles and graphene. © 2013 American Chemical Society.

2D Monolayer MoS2–Carbon Interoverlapped Superstructure: Engineering Ideal Atomic Interface for Lithium Ion Storage: Engineering Ideal Atomic Interface for Lithium Ion Storage

A novel strategy for the controlled synthesis of 2D MoS<inf>2</inf>/C hybrid nanosheets consisting of the alternative layer-by-layer interoverlapped single-layer MoS<inf>2</inf> and mesoporous carbon (m-C) is demonstrated. Such special hybrid nanosheets with a maximized MoS<inf>2</inf>/m-C interface contact show very good performance for lithium-ion batteries in terms of high reversible capacity, excellent rate capability, and outstanding cycling stability.

Hydrogel-forming microneedle arrays: Potential for use in minimally-invasive lithium monitoring

We describe, for the first time, hydrogel-forming microneedle (MN) arrays for minimally-invasive extraction and quantification of lithium in vitro and in vivo. MN arrays, prepared from aqueous blends of hydrolysed poly(methyl-vinylether-co-maleic anhydride) and crosslinked by poly(ethyleneglycol), imbibed interstitial fluid (ISF) upon skin insertion. Such MN were always removed intact. In vitro, mean detected lithium concentrations showed no significant difference following 30 min MN application to excised neonatal porcine skin for lithium citrate concentrations of 0.9 and 2 mmol/l. However, after 1 h application, the mean lithium concentrations extracted were significantly different, being appropriately concentration-dependent. In vivo, rats were orally dosed with lithium citrate equivalent to 15 mg/kg and 30 mg/kg lithium carbonate, respectively. MN arrays were applied 1 h after dosing and removed 1 h later. The two groups, having received different doses, showed no significant difference between lithium concentrations in serum or MN. However, the higher dosed rats demonstrated a lithium concentration extracted from MN arrays equivalent to a mean increase of 22.5 % compared to rats which received the lower dose. Hydrogel-forming MN clearly have potential as a minimally-invasive tool for lithium monitoring in out-patient settings. We will now focus on correlation of serum and MN lithium concentrations.

Effect of cation structure on the oxygen solubility and diffusivity in a range of bis{(trifluoromethyl)sulfonyl}imide anion based ionic liquids for lithium-air battery electrolytes

This paper reports on the solubility and diffusivity of dissolved oxygen in a series of ionic liquids (ILs) based on the bis{(trifluoromethyl)sulfonyl}imide anion with a range of related alkyl and ether functionalised cyclic alkylammonium cations. Cyclic voltammetry has been used to observe the reduction of oxygen in ILs at a microdisk electrode and chronoamperometric measurements have then been applied to simultaneously determine both the concentration and the diffusion coefficient of oxygen in the different ILs. The viscosity of the ILs and the calculated molar volume and free volume is also reported. It is found that, within this class of ILs, the oxygen diffusivity generally increases with decreasing viscosity of the neat IL. An inverse relationship between oxygen solubility and IL free volume is reported for the two IL families implying oxygen is not simply occupying the available empty space. In addition, it is reported that the introduction of ether-group into the IL cation structure promotes the diffusivity of dissolved oxygen but reduces the solubility of the gas.

Collisional-radiative study of lithium plasmas

The sensitivity of lithium plasma models to the underlying atomic data is investigated. Collisional-radiative modeling is carried out with both the Los Alamos and ADAS suite of codes. The effects of plane-wave Born, distorted-wave, and nonperturbative R -matrix with pseudostates and time-dependent close-coupling electron impact atomic data on derived plasma quantities such as the ionization balance and radiated power are studied. Density and temperature regimes are identified where nonperturbative excitation and ionization rate coefficients must be used. The electron temperature and density ranges investigated were 0.2 eV<or = T(e) <or =90 eV and 10(10) cm(-3) <or = N(e) <or = 10(14) cm(-3).

Development of lithium disilicate based glass-ceramics

O principal objectivo deste estudo foi o desenvolvimento de vitrocerâmicos à base de dissilicato de lítio no sistema Li2O-K2O-Al2O3-SiO2 contendo uma razão molar SiO2/Li2O muito afastada da do dissilicato de lítio (Li2Si2O5) usando composições simples e a técnica tradicional de fusão-vazamento de vidro de forma a obter materiais com propriedades mecânicas, térmicas, químicas e eléctricas superiores que permitam a utilização destes materiais em diversas aplicações funcionais. Investigou-se o fenómeno de separação de fases, a cristalização e as relações estrutura-propriedades de vidros nos sistemas Li2O-SiO2, Li2O-Al2O3-SiO2 e Li2O-K2O-Al2O3-SiO2. Os vidros nos sistemas Li2O-SiO2 e Li2O-Al2O3-SiO2 apresentaram fraca densificação e resultaram em materiais frágeis, contrastando com a boa sinterização dos vidros no sistema Li2O-K2O-Al2O3-SiO2. Pequenas adições de Al2O3 e K2O ao sistema Li2O-SiO2 permitiram controlar a separação de fases devido à formação de espécies de Al(IV) que confirmaram o papel de Al2O3 como formador de rede. Os compactos de pó de vidro das composições contendo Al2O3 e K2O tratados termicamente resultaram em vitrocerâmicos bem densificados, apresentando dissilicato de lítio como a principal fase cristalina, e valores de resistência mecânica à flexão, resistência química e condutividade eléctrica (173-224 MPa, 25-50 mg/cm2 e ~2´10-18 S/cm, respectivamente) que possibilitam a utilização destes materiais em diversas aplicações funcionais. A adição de P2O5, TiO2 e ZrO2 ao sistema Li2O-K2O-Al2O3-SiO2 como agentes nucleantes revelou que os vidros contendo apresentaram cristalização em volume, com a formação de metassilicato de lítio a temperaturas mais baixas e dissilicato de lítio para as temperaturas mais elevadas, enquanto a adição de zircónia reduz o grau de segregação, aumenta a polimerização da matriz vítrea e desloca o valor de Tg para temperaturas superiores, inibindo a cristalização.