Electronic structure and chemical bonding of a graphene oxide-sulfur nanocomposite for use in superior performance lithium-sulfur cells.

We have investigated the chemical bonding and electronic structure of a graphene oxide-sulfur (GO-S) nanocomposite by X-ray Photoelectron Spectroscopy (XPS), Near-edge X-ray Absorption Fine Structure (NEXAFS), and X-ray Emission Spectroscopy (XES). The nanocomposite, synthesized by a chemical reaction-deposition approach followed by low temperature thermal treatment, is composed of a thin and uniform sulfur film anchored on a graphene oxide (GO) sheet. The GO is partially reduced during the chemical synthesis process, resulting in the appearance of a C-H bond and an increase in the ordering of GO sheets. The moderate chemical interactions between sulfur and GO can preserve the intrinsic electronic structure of GO, and on the other hand, immobilize the sulfur on the GO sheets, which should be responsible for the excellent electrochemical performance of the lithium-sulfur cells by using the GO-S nanocomposite as the cathode material.

SnS2 nanoparticle loaded graphene nanocomposites for superior energy storage.

SnS2 nanoparticle-loaded graphene nanocomposites were synthesized via one-step hydrothermal reaction. Their electrochemical performance was evaluated as the anode for rechargeable lithium-ion batteries after thermal treatment in an Ar environment. The electrochemical testing results show a high reversible capacity of more than 800 mA h g(-1) at 0.1 C rate and 200 mA h g(-1) for up to 5 C rate. The cells also exhibit excellent capacity retention for up to 90 cycles even at a high rate of 2 C. This electrochemical behavior can be attributed to the well-defined morphology and nanostructures of these as-synthesized nanocomposites, which is characterized by high-resolution transmission electron microscopy and electron energy-loss spectroscopy.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells.

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Here, we use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach enabled us to obtain a uniform and thin (around tens of nanometers) sulfur coating on graphene oxide sheets by a simple chemical reaction-deposition strategy and a subsequent low-temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides enabled us to demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mA h g(-1), and stable cycling for more than 50 deep cycles at 0.1C (1C = 1675 mA g(-1)).

Fe3O4 nanoparticle-integrated graphene sheets for high-performance half and full lithium ion cells.

We synthesized Fe(3)O(4) nanoparticle/reduced graphene oxide (RGO-Fe(3)O(4)) nanocomposites and evaluated their performance as anodes in both half and full coin cells. The nanocomposites were synthesized through a chemical co-precipitation of Fe(2+) and Fe(3+) in the presence of graphene oxides within an alkaline solution and a subsequent high-temperature reduction reaction in argon (Ar) environment. The morphology and microstructures of the fabricated RGO-Fe(3)O(4) nanocomposites were characterized using various techniques. The results indicated that the Fe(3)O(4) nanoparticles had relatively homogeneous dispersions on the RGO sheet surfaces. These as-synthesized RGO-Fe(3)O(4) nanocomposites were used as anodes for both half and full lithium-ion cells. Electrochemical measurement results exhibit a high reversible capacity which is about two and a half times higher than that of graphite-based anodes at a 0.05C rate, and an enhanced reversible capacity of about 200 mAh g(-1) even at a high charge/discharge rate of 10C (9260 mA g(-1)) in half cells. Most important of all, these fabricated novel nanostructures also show exceptional capacity retention with the assembled RGO-Fe(3)O(4)/LiNi(1/3)Mn(1/3)Co(1/3)O(2) full cell at different C rates. This outstanding electrochemical behavior can be attributed to the unique microstructure, morphology, texture, surface properties of the nanocomposites, and combinative effects from the different chemical composition in the nanocomposites.

Assembly of carbon-SnO2 core-sheath composite nanofibers for superior lithium storage.

Protective coating: Carbon-SnO(2) core-sheath composite nanofibers are synthesized through the creative combination of electrospinning and electrodeposition processes (see figure). They display excellent electrochemical performance when directly used as binder-free anodes for rechargeable lithium ion batteries.

Fabrication of porous carbon nanofibers and their application as anode materials for rechargeable lithium-ion batteries.

Porous carbon nanofibers were prepared by the electrospinning of a bicomponent polymer solution, followed by thermal treatments under different atmospheres. The surface morphology, thermal properties, and crystalline features of these nanofibers were characterized using various analytic techniques, and it was found that they were formed with turbostratically disordered graphene sheets and had small pores and large surface areas. The unique structure of these porous carbon nanofibers resulted in good electrochemical performance such as high reversible capacity and good cycle stability when they were used as anodes for rechargeable lithium-ion batteries.

Characterization of nanostructure and cell compatibility of polyaniline films with different dopant acids.

Polyaniline (PANi) films were prepared by direct polymerizing deposition with four different kinds of acids as dopants or were prepared by a casting method on the surface of a polytetrafluoroethylene substrate. The properties of PANi films were characterized using atomic force microscopy, electrical conductivity measurements, and water contact angle measurements. Unlike the casting PANi film, experimental results indicated that the synthesized PANi films had a similar nanostructure as that of average nanoparticles (approximate diameter of 30-50 nm). To investigate the potential usefulness of PANi films in biomedical applications, we also studied their biocompatibility through the adhesion and proliferation properties of PC-12 pheochromocytoma cells. All the films were found to be biocompatible and allowed cell attachment and proliferation. However, the synthesized films have a much higher ability for cell adhesion than the casting film. After 4 days of culture on different PANi films, the cells formed more confluent monolayers on the synthesized PANi films than on the casting films. These results demonstrate that the PANi films could be used to culture neurotic cells and that their surface architecture on the nanoscale may affect cell function such as attachment and proliferation.

Film from peroxidation of an amino phospholipid and its biocompatibility.

A new kind of phospholipid product with fluorescence was derived from autoxidation of an aminophospholipid, L-alpha-phosphatidylethanolamine dilinoleoyl in solid film state. Atomic force microscopy showed that the film product was composed of round and elliptical vesicles with diameters of about 20-45 nm. The product was difficult to dissolve in water and most organic solvents. Fourier transform infrared spectroscopy, solid-state (13)C NMR, and solid-state (31)P NMR indicated that the unsaturated double carbon bond decreased with the reaction, and polymerization within/between phospholipid molecules occurred. Endothelial cells from human vein seeded onto the film showed the highest proliferating activity compared with seeding onto Corning culture plate, glass plate, or phospholipid film with phosphorylcholine head group, as evaluated by 3-(4,5-timethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay (p < 0.001). The hemocompatibility of the film was also assessed by platelet adhesion and protein adsorption. The results suggest that the product has potential applications as a new biomaterial coating.

Reduced Graphene Oxide/Tin-Antimony Nanocomposites as Anode Materials for Advanced Sodium-Ion Batteries.

Reduced graphene oxides loaded with tin-antimony alloy (RGO-SnSb) nanocomposites were synthesized through a hydrothermal reaction and the subsequent thermal reduction treatments. Transmission electron microscope images confirm that SnSb nanoparticles with an average size of about 20-30 nm are uniformly dispersed on the RGO surfaces. When they were used as anodes for rechargeable sodium (Na)-ion batteries, these as-synthesized RGO-SnSb nanocomposite anodes delivered a high initial reversible capacity of 407 mAh g(-1), stable cyclic retention for more than 80 cycles and excellent cycle stability at ultra high charge/discharge rates up to 30C. The significantly improved performance of the synthesized RGO-SnSb nanocomposites as Na-ion battery anodes can be attributed to the synergetic effects of RGO-based flexible framework and the nanoscale dimension of the SnSb alloy particles (<30 nm). Nanosized intermetallic SnSb compounds can exhibit improved structural stability and conductivity during charge and discharge reactions compared to the corresponding individuals (Sn and Sb particles). In the meantime, RGO sheets can tightly anchor SnSb alloy particles on the surfaces, which can not only effectively suppress the agglomeration of SnSb particles but also maintain excellent electronic conduction. Furthermore, the mechanical flexibility of the RGO phase can accommodate the volume expansion and contraction of SnSb particles during the prolonged cycling, therefore, improve the electrode integrity mechanically and electronically. All of these contribute to the electrochemical performance improvements of the RGO-SnSb nanocomposite-based electrodes in rechargeable Na-ion batteries.

Controlling SEI formation on SnSb-porous carbon nanofibers for improved Na ion storage.

Porous carbon nanofiber (CNF)-supported tin-antimony (SnSb) alloys are synthesized and applied as a sodium-ion battery anode. The chemistry and morphology of the solid electrolyte interphase (SEI) film and its correlation with the electrode performance are studied. The addition of fluoroethylene carbonate (FEC) in the electrolyte significantly reduces electrolyte decomposition and creates a very thin and uniform SEI layer on the cycled electrode surface, which an promote the kinetics of Na-ion migration/transportation, leading to excellent electrochemical performance.

Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures.

Lithium-sulphur batteries have high theoretical energy density and potentially low cost, but significant challenges such as severe capacity degradation prevent its widespread adoption. Here we report a new design of lithium-sulphur battery using electrically connected graphite and lithium metal as a hybrid anode to control undesirable surface reactions on lithium. Lithiated graphite placed in front of the lithium metal functions as an artificial, self-regulated solid electrolyte interface layer to actively control the electrochemical reactions and minimize the deleterious side reactions, leading to significant performance improvements. Lithium-sulphur cells incorporating this hybrid anodes deliver capacities of >800 mAh g(-1) for 400 cycles at a high rate of 1,737 mA g(-1), with only 11% capacity fade and a Coulombic efficiency >99%. This simple hybrid concept may also provide scientific strategies for protecting metal anodes in other energy-storage devices.

Carbon nanotube-loaded electrospun LiFePO4/carbon composite nanofibers as stable and binder-free cathodes for rechargeable lithium-ion batteries.

LiFePO(4)/CNT/C composite nanofibers were synthesized by using a combination of electrospinning and sol-gel techniques. Polyacrylonitrile (PAN) was used as the electrospinning media and carbon source. Functionalized CNTs were used to increase the conductivity of the composite. LiFePO(4) precursor materials, PAN and functionalized CNTs were dissolved or dispersed in N,N-dimethylformamide separately and they were mixed before electrospinning. LiFePO(4) precursor/CNT/PAN composite nanofibers were then heat-treated to obtain LiFePO(4)/CNT/C composite nanofibers. Fourier transform infrared spectroscopy measurements were done to demonstrate the functionalization of CNTs. The structure of LiFePO(4)/CNT/C composite nanofibers was determined by X-ray diffraction analysis. The surface morphology and microstructure of LiFePO(4)/CNT/C composite nanofibers were characterized using scanning electron microscopy and transmission electron microscopy. Electrochemical performance of LiFePO(4)/CNT/C composite nanofibers was evaluated in coin-type cells. Functionalized CNTs were found to be well-dispersed in the carbonaceous matrix and increased the electrochemical performance of the composite nanofibers. As a result, cells using LiFePO(4)/CNT/C composite nanofibers have good performance, in terms of large capacity, extended cycle life, and good rate capability.

α-Fe2O3 nanoparticle-loaded carbon nanofibers as stable and high-capacity anodes for rechargeable lithium-ion batteries.

α-Fe(2)O(3) nanoparticle-loaded carbon nanofiber composites were fabricated via electrospinning FeCl(3)·6H(2)O salt-polyacrylonitrile precursors in N,N-dimethylformamide solvent and the subsequent carbonization in inert gas. Scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and elemental analysis were used to study the morphology and composition of α-Fe(2)O(3)-carbon nanofiber composites. It was indicated that α-Fe(2)O(3) nanoparticles with an average size of about 20 nm have a homogeneous dispersion along the carbon nanofiber surface. The resultant α-Fe(2)O(3)-carbon nanofiber composites were used directly as the anode material in rechargeable lithium half cells, and their electrochemical performance was evaluated. The results indicated that these α-Fe(2)O(3)-carbon nanofiber composites have high reversible capacity, good capacity retention, and acceptable rate capability when used as anode materials for rechargeable lithium-ion batteries.

Electrospun carbon-tin oxide composite nanofibers for use as lithium ion battery anodes.

Composite carbon-tin oxide (C-SnO(2)) nanofibers are prepared by two methods and evaluated as anodes in lithium-ion battery half cells. Such an approach complements the long cycle life of carbon with the high lithium storage capacity of tin oxide. In addition, the high surface-to-volume ratio of the nanofibers improves the accessibility for lithium intercalation as compared to graphite-based anodes, while eliminating the need for binders or conductive additives. The composite nanofibrous anodes have first discharge capacities of 788 mAh g(-1) at 50 mA g(-1) current density, which are greater than pure carbon nanofiber anodes, as well as the theoretical capacity of graphite (372 mAh g(-1)), the traditional anode material. In the first protocol to fabricate the C-SnO(2) composites, tin sulfate is directly incorporated within polyacrylonitrile (PAN) nanofibers by electrospinning. During a thermal treatment the tin salt is converted to tin oxide and the polymer is carbonized, yielding carbon-SnO(2) nanofibers. In the second approach, we soak the nanofiber mats in tin sulfate solutions prior to the final thermal treatment, thereby loading the outer surfaces with SnO(2) nanoparticles and raising the tin content from 1.9 to 8.6 wt %. Energy-dispersive spectroscopy and X-ray diffraction analyses confirm the formation of conversion of tin sulfate to tin oxide. Furthermore, analysis with Raman spectroscopy reveals that the additional salt soak treatment from the second fabrication approach increases in the disorder of the carbon structure, as compared to the first approach. We also discuss the performance of our C-SnO(2) compared with its theoretical capacity and other nanofiber electrode composites previously reported in the literature.

Sulfonated polystyrene fiber network-induced hybrid proton exchange membranes.

A novel type of hybrid membrane was fabricated by incorporating sulfonated polystyrene (S-PS) electrospun fibers into Nafion for the application in proton exchange membrane fuel cells. With the introduction of S-PS fiber mats, a large amount of sulfonic acid groups in Nafion aggregated onto the interfaces between S-PS fibers and the ionomer matrix, forming continuous pathways for facile proton transport. The resultant hybrid membranes had higher proton conductivities than that of recast Nafion, and the conductivities were controlled by selectively adjusting the fiber diameters. Consequently, hybrid membranes fabricated by ionomers, such as Nafion, incorporated with ionic-conducting nanofibers established a promising strategy for the rational design of high-performance proton exchange membranes.

Preparation and characterization of silica nanoparticulate-polyacrylonitrile composite and porous nanofibers.

In this study, polyacrylonitrile (PAN) composite nanofibers containing different amounts of silica nanoparticulates have been obtained via electrospinning. The surface morphology, thermal properties and crystal structure of PAN/silica nanofibers are characterized using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, wide-angle x-ray diffraction (WAXD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results indicate that the addition of silica nanoparticulates affects the structure and properties of the nanofibers. In addition to PAN/silica composite nanofibers, porous PAN nanofibers have been prepared by selective removal of the silica component from PAN/silica composite nanofibers using hydrofluoric (HF) acid. ATR-FTIR and thermal gravimetric analysis (TGA) experiments validate the removal of silica nanoparticulates by HF acid, whereas SEM and TEM results reveal that the porous nanofibers obtained from composite fibers with higher silica contents exhibited more nonuniform surface morphology. The Brunauer-Emmett-Teller (BET) surface area of porous PAN nanofibers made from PAN/silica (5 wt%) composite precursors is higher than that of pure nonporous PAN nanofibers.