Porous Flower-like alpha-Fe2O3 Nanostructure: A High Performance Anode Material for Lithium-ion Batteries

Porous flower-like alpha-Fe2O3 nanostructures have been synthesized by ethylene glycol mediated iron alkoxide as an intermediate and studied as an anode material of Li-ion battery. The iron alkoxide precursor is heated at different temperatures from 300 to 700 degrees C. The alpha-Fe2O3 samples possess porosity and high surface area. There is a decrease in pore volume as well as surface area by increasing the preparation temperature. The reversible cycling properties of the alpha-Fe2O3 nanostructures have been evaluated by cyclic voltammetry, galvanostatic charge discharge cycling, and galvanostatic intermittent titration measurements at ambient temperature. The initial discharge capacity values of 1063, 1168,1183, 1152 and 968 mAh g(-1) at a specific current of 50 mA g(-1) are obtained for the samples prepared at 300, 400, 500, 600 and 700 degrees C, respectively. The samples prepared at 500 and 600 degrees C exhibit good cycling performance with high rate capability. The high rate capacity is attributed to porous nature of the materials. As the iron oxides are inexpensive and environmental friendly, the alpha-Fe2O3 has potential application as anode material for rechargeable Li batteries. (C) 2015 Elsevier Ltd. All rights reserved.

Na2.44Mn1.79(SO4)(3): a new member of the alluaudite family of insertion compounds for sodium ion batteries

Sodium-ion batteries have been extensively pursued as economic alternatives to lithium-ion batteries. Investigating the polyanion chemistry, alluaudite structured Na2Fe2II(SO4)(3) has been recently discovered as a 3.8 V positive electrode material (Barpanda et al., Nature Commun., 5: 4358, 2014). Registering the highest ever Fe-III/Fe-II redox potential (vs. Na/Na+) and formidable energy density, it has opened up a new polyanion family for sodium batteries. Exploring the alluaudite family, here we report isotypical Na2+2xMn2-xII(SO4)(3) (x = 0.22) as a novel high-voltage cathode material for the first time. Following low-temperature (ca. 350 degrees C) solid-state synthesis, the structure of this new alluaudite compound has been solved adopting a monoclinic framework (s.g. C2/c) showing antiferromagnetic ordering at 3.4 K. Synergising experimental and ab initio DFT investigation, Na2+2xMn2-xII(SO4)(3) has been found to be a potential high-voltage (ca. 4.4 V) cathode material for sodium batteries.

Fracture of materials undergoing solid-solid phase transformation

A large number of technologically important materials undergo solid-solid phase transformations. Examples range from ferroelectrics (transducers and memory devices), zirconia (Thermal Barrier Coatings) to nickel superalloys and (lithium) iron phosphate (Li-ion batteries). These transformations involve a change in the crystal structure either through diffusion of species or local rearrangement of atoms. This change of crystal structure leads to a macroscopic change of shape or volume or both and results in internal stresses during the transformation. In certain situations this stress field gives rise to cracks (tin, iron phosphate etc.) which continue to propagate as the transformation front traverses the material. In other materials the transformation modifies the stress field around cracks and effects crack growth behavior (zirconia, ferroelectrics). These observations serve as our motivation to study cracks in solids undergoing phase transformations. Understanding these effects will help in improving the mechanical reliability of the devices employing these materials.

In this thesis we present work on two problems concerning the interplay between cracks and phase transformations. First, we consider the directional growth of a set of parallel edge cracks due to a solid-solid transformation. We conclude from our analysis that phase transformations can lead to formation of parallel edge cracks when the transformation strain satisfies certain conditions and the resulting cracks grow all the way till their tips cross over the phase boundary. Moreover the cracks continue to grow as the phase boundary traverses into the interior of the body at a uniform spacing without any instabilities. There exists an optimal value for the spacing between the cracks. We ascertain these conclusion by performing numerical simulations using finite elements.

Second, we model the effect of the semiconducting nature and dopants on cracks in ferroelectric perovskite materials, particularly barium titanate. Traditional approaches to model fracture in these materials have treated them as insulators. In reality, they are wide bandgap semiconductors with oxygen vacancies and trace impurities acting as dopants. We incorporate the space charge arising due the semiconducting effect and dopant ionization in a phase field model for the ferroelectric. We derive the governing equations by invoking the dissipation inequality over a ferroelectric domain containing a crack. This approach also yields the driving force acting on the crack. Our phase field simulations of polarization domain evolution around a crack show the accumulation of electronic charge on the crack surface making it more permeable than was previously believed so, as seen in recent experiments. We also discuss the effect the space charge has on domain formation and the crack driving force.

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)(3)(2+) immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.

An electrochemical study of prussian blue microcrystallines mixed in PEO400 polymer electrolyte by solid-state voltammetry

The electrochemistry of Prussian blue mixed in a polymer medium containing MClO4 (M = Li+, Na+, K+, TBA(+)) as the supporting electrolyte was studied by means of solid-state voltammetry. This approach is new in Prussian blue studies. The behavior of PB in polymer electrolytes is somewhat similar to the well-known behavior for an electrochemically synthesized PB film in aqueous media. Besides, K+, Li+ and Na+ ions can also transport through the crystal of PB because of its zeolitic nature. The transport of TBA(+) ions is possible. Kinetic control lies in the diffusion of cations in and out of the lattice of Prussian blue. Reduction waves of Prussian blue depend on both the size and type of cations. PB is very stable upon electrochemical cycling in polymer electrolytes and air. This system may be used in rechargeable batteries and electrochromic devices.

Fabrication and characterization of doped and porous silicon nanowires as anodes for lithium ion batteries

By using Si(100) with different dopant type (n++-type (As) or p-type (B)), it is shown how metal-assisted chemically (MAC) etched silicon nanowires (Si NWs) can form with rough outer surfaces around a solid NW core for p-type NWs, and a unique, defined mesoporous structure for highly doped n-type NWs. High resolution electron microscopy techniques were used to define the characteristic roughening and mesoporous structure within the NWs and how such structures can form due to a judicious choice of carrier concentration and dopant type. Control of roughness and internal mesoporosity is demonstrated during the formation of Si NWs from highly doped n-type Si(100) during electroless etching through a systematic investigation of etching parameters (etching time, AgNO3 concentration, %HF and temperature). Raman scattering measurements of the transverse optical phonon confirm quantum size effects and phonon scattering in mesoporous wires associated with the etching condition, including quantum confinement effects for the nanocrystallites of Si comprising the internal structure of the mesoporous NWs. Laser power heating of NWs confirms phonon confinement and scattering from internal mesoporosity causing reduced thermal conductivity. The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. X-ray photo-electron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity. The effect of dopant, doping density and porosity of MAC etched Si NWs are investigated. The CV response is shown to change in area (current density) with increasing NW length and in profile shape with a changing porosity of the Si NWs. The CV response also changes with scan rate indicative of a transition from intercalation or alloying reactions, to pseudocapactive charge storage at higher scan rates and for p-type NWs. SEM and TEM show a change in structure of the NWs after Li insertion and extraction due to expansion and contraction of the Si NWs. Galvanostatic measurements show the cycling behavior and the Coulombic efficiency of the Si NWs in comparison to their bulk counterparts.

Solid-state analysis of low-melting 1,3-dialkylimidazolium hexafluorophosphate salts (ionic liquids) by combined x-ray crystallographic and computational analyses

The interactions of ions in the solid state for a series of representative 1,3-dialkylimidazolium hexafluorophosphate salts (either ionic liquids or closely related) have been examined by crystallographic analysis, combined with the theoretical estimation of crystal-packing densities and lattice-interaction energies. Efficient close-packing of the ions in the crystalline states is observed, but there was no compelling evidence for specific directional hydrogen-bonding to the hexafluorophosphate anions or the formation of interstitial voids. The close-packing efficiency is supported by the theoretical calculation of ion volumes, crystal lattice energies, and packing densities, which correlated well with experimental data. The crystal density of the salts can be predicted accurately from the summation of free ion volumes and lattice energies calculated. Of even more importance for future work, on these and related salts, the solid-state density of 1,3-dialkylimidazolium hexafluorophosphate salts can be predicted with reasonable accuracy purely on the basis of on ab initio free ion volumes, and this allows prediction of lattice energies without necessarily requiring the crystal structures.

Low pressure carbon dioxide solubility in pure electrolyte solvents for lithium-ion batteries as a function of temperature. Measurement and prediction

Experimental values for the carbon dioxide solubility in eight pure electrolyte solvents for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ?-butyrolactone (?BL), ethyl acetate (EA) and methyl propionate (MP) – are reported as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility data, the Henry’s law constant of the carbon dioxide in these solvents was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOthermX software and those calculated by the Peng–Robinson equation of state implemented into Aspen plus. From this work, it appears that the CO2 solubility is higher in linear carbonates (such as DMC, EMC, DEC) than in cyclic ones (EC, PC, ?BL). Furthermore, the highest CO2 solubility was obtained in MP and EA solvents, which are comparable to the solubility values reported in classical ionicliquids. The precision and accuracy of the experimental values, considered as the per cent of the relative average absolute deviations of the Henry’s law constants from appropriate smoothing equations and from literature values, are close to (1% and 15%), respectively. From the variation of the Henry’s law constants with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs free energy, the enthalpy, and the entropy are calculated, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Low pressure methane solubility in lithium-ion batteries based solvents and electrolytes as a function of temperature. Measurement and prediction

The methane solubility in five pure electrolyte solvents and one binary solvent mixture for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and the (50:50 wt%) mixture of EC:DMC was studied experimentally at pressures close to atmospheric and as a function of temperature between (280 and 343) K by using an isochoric saturation technique. The effect of the selected anions of a lithium salt LiX (X = hexafluorophosphate,

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.

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).

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.

A detailed study of the lithiation of iron phosphate as well as the development of a novel synthesis of lithium iron silicate as cathode material for lithium-ion batteries

Dans cette thèse nous démontrons le travail fait sur deux matériaux de cathodes pour les piles lithium-ion. Dans la première partie, nous avons préparé du phosphate de fer lithié (LiFePO4) par deux méthodes de lithiation présentées dans la littérature qui utilisent du phosphate de fer (FePO4) amorphe comme précurseur. Pour les deux méthodes, le produit obtenu à chaque étape de la synthèse a été analysé par la spectroscopie Mössbauer ainsi que par diffraction des rayons X (DRX) pour mieux comprendre le mécanisme de la réaction. Les résultats de ces analyses ont été publiés dans Journal of Power Sources. Le deuxième matériau de cathode qui a été étudié est le silicate de fer lithié (Li2FeSiO4). Une nouvelle méthode de synthèse a été développée pour obtenir le silicate de fer lithié en utilisant des produits chimiques peu couteux ainsi que de l’équipement de laboratoire de base. Le matériau a été obtenu par une synthèse à l’état solide. Les performances électrochimiques ont été obtenues après une étape de broyage et un dépôt d’une couche de carbone. Un essai a été fait pour synthétiser une version substituée du silicate de fer lithié dans le but d’augmenter les performances électrochimiques de ce matériau.

Low cost synthesis of cathode and anode materials for lithium-ion batteries

Dans cette thèse, nous démontrons des travaux sur la synthèse à faible coût des matériaux de cathode et l'anode pour les piles lithium-ion. Pour les cathodes, nous avons utilisé des précurseurs à faible coût pour préparer LiFePO4 et LiFe0.3Mn0.7PO4 en utilisant une méthode hydrothermale. Tout d'abord, des matériaux composites (LiFePO4/C) ont été synthétisés à partir d'un précurseur de Fe2O3 par une procédé hydrothermique pour faire LiFePO4(OH) dans une première étape suivie d'une calcination rapide pour le revêtement de carbone. Deuxièmement, LiFePO4 avec une bonne cristallinité et une grande pureté a été synthétisé en une seule étape, avec Fe2O3 par voie hydrothermale. Troisièmement, LiFe0.3Mn0.7PO4 a été préparé en utilisant Fe2O3 et MnO comme des précurseurs de bas coûts au sein d'une méthode hydrothermale synthétique. Pour les matériaux d'anode, nous avons nos efforts concentré sur un matériau d'anode à faible coût α-Fe2O3 avec deux types de synthèse hydrothermales, une a base de micro-ondes (MAH) l’autre plus conventionnelles (CH). La nouveauté de cette thèse est que pour la première fois le LiFePO4 a été préparé par une méthode hydrothermale en utilisant un précurseur Fe3+ (Fe2O3). Le Fe2O3 est un précurseur à faible coût et en combinant ses coûts avec les conditions de synthèse à basse température nous avons réalisé une réduction considérable des coûts de production pour le LiFePO4, menant ainsi à une meilleure commercialisation du LiFePO4 comme matériaux de cathode dans les piles lithium-ion. Par cette méthode de préparation, le LiFePO4/C procure une capacité de décharge et une stabilité de cycle accrue par rapport une synthétisation par la méthode à l'état solide pour les mêmes précurseurs Les résultats sont résumés dans deux articles qui ont été récemment soumis dans des revues scientifiques.