Synthesis of Co3O4 nano-octahedra enclosed by {111} facets and their excellent lithium storage properties as anode material of lithium ion batteries

Abstract
Nano-sized(nO-Co3O4, 387nm)andmicron-sized(mO-Co3O4, 6.65 mm) Co3O4 octahedraenclosedby
{111}facetshavebeenbothsynthesizedthroughawetchemicalmethodfollowedbythermal
treatment,andservedasanodematerialoflithium ionbatteries(LIBs).Electrochemicalresults
demonstratethatthenO-Co3O4 showsexcellentlongcyclabilityandratecapability.ThenO-Co3O4
candeliverastablechargecapacityashighas955.5mAhg1 upto200cycleswithoutnoticeable
capacityfadingatacharge/dischargecurrentdensityof0.1Ag1 (ca. 0.11C).Theexcellent
electrochemicalperformanceisascribedtothenano-sizeandthe{111}facetsthatenclosethe
octahedra. WhilethemO-Co3O4 could onlymaintain288.5mAhg1 after 200cycles,illustratingvery
poorcyclingperformance,whichisascribedtothelargeparticlesizethatmaycausehugevolume
changeduringrepeatedcharging/discharging process.TheresultsrevealthattheCo3O4 nano-
octahedrawouldbeapromisinganodematerialforthenext-generationofLIBs.

Deep eutectic solvents based on N-methylacetamide and a lithium salt as suitable electrolytes for lithium-ion batteries

In this work, we present a study on the physical and electrochemical properties of three new Deep Eutectic Solvents (DESs) based on N-methylacetamide (MAc) and a lithium salt (LiX, with X = bis[(trifluoromethyl)sulfonyl]imide, TFSI; hexafluorophosphate, PF; or nitrate, NO). Based on DSC measurements, it appears that these systems are liquid at room temperature for a lithium salt mole fraction ranging from 0.10 to 0.35. The temperature dependences of the ionic conductivity and the viscosity of these DESs are correctly described by using the Vogel-Tammann-Fulcher (VTF) type fitting equation, due to the strong interactions between Li, X and MAc in solution. Furthermore, these electrolytes possess quite large electrochemical stability windows up to 4.7-5 V on Pt, and demonstrate also a passivating behavior toward the aluminum collector at room temperature. Based on these interesting electrochemical properties, these selected DESs can be classified as potential and promising electrolytes for lithium-ion batteries (LIBs). For this purpose, a test cell was then constructed and tested at 25 °C, 60 °C and 80 °C by using each selected DES as an electrolyte and LiFePO (LFP) material as a cathode. The results show a good compatibility between each DES and LFP electrode material. A capacity of up to 160 mA h g with a good efficiency (99%) is observed in the DES based on the LiNO salt at 60 °C despite the presence of residual water in the electrolyte. Finally preliminary tests using a LFP/DES/LTO (lithium titanate) full cell at room temperature clearly show that LiTFSI-based DES can be successfully introduced into LIBs. Considering the beneficial properties, especially, the cost of these electrolytes, such introduction could represent an important contribution for the realization of safer and environmentally friendly LIBs. © 2013 the Owner Societies.

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 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. 

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.

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.

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.

Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.

The enhancement of lithium ion dissociation in polyelectrolyte gels on the addition of ceramic nano-fillers

Nano-particle oxide fillers including TiO₂, SiO₂ and Al₂O₃ have previously been shown to have a significant affect on the properties of both polymer and polymer gel electrolytes. In some cases, conductivity increases of one order of magnitude have been reported in crystalline PEO–base complexes. In this work, we report the effects of TiO₂ and SiO₂ on a poly(Li-AMPS)-based gel polyelectrolyte. Impedance spectroscopy and pfg-NMR spectroscopy indicates an increase in the number of available charge carriers with the addition of filler. An ideal amount of ceramic filler has been identified, with additional filler only saturating the system and reducing the conductivity below that of the pristine polyelectrolyte system. SEM micrographs suggest a model whereby the filler interacts readily with the sulfonate group; the surface area of the filler being an important factor.

Lithium-polymer battery based on an ionic liquid–polymer electrolyte composite for room temperature applications

A lithium-polymer battery based on an ionic liquid–polymer electrolyte (IL–PE) composite membrane operating at room temperature is described. Utilizing a polypyrrole coated LiV₃O₈ cathode material, the cell delivers >200 mAh g⁻¹ with respect to the mass of the cathode material. Discharge capacity is slightly higher than those observed for this cathode material in standard aprotic electrolytes; it is thought that this is the result of a lower solubility of the LiV₃O₈ material in the IL–PE composite membrane.

Lithium ion mobility in poly(vinyl alcohol) based polymer electrolytes as determined by 7Li NMR spectroscopy

Solvent-free polymer electrolytes based on poly(vinyl alcohol) (PVA) and LiCF₃SO₃ have shown relatively high conductivities (10⁻⁸-10⁻⁴ S cm⁻¹), with Arrhenius temperature dependence below the differential scanning calorimeter (DSC) glass transition temperature (343 K). This behaviour is in stark contrast to traditional polymer electrolytes in which the conductivity reflects VTF behaviour. ⁷Li nuclear magnetic resonance (NMR) spectroscopy has been employed to develop a better understanding of the conduction mechanism. Variable temperature NMR has indicated that, unlike traditional polymer electrolytes where the linewidth reaches a rigid lattice limit near T_g, the lithium linewidths show an exponential decrease with increasing temperature between 260 and 360 K. The rigid lattice limit appears to be below 260 K. Consequently, the mechanism for ion conduction appears to be decoupled from the main segmental motions of the PVA. Possible mechanisms include ion hopping, proton conduction or ionic motion assisted by secondary polymer relaxations.

Solid state lithium ion conduction in pyrrolidinium imide–lithium imide salt mixtures

The properties of the binary salt system based on mixtures of methyl ethyl pyrrolidinium bis(trifluoromethane sulfonyl) imide (P₁₂) and lithium bis(trifluoromethane sulfonyl) imide (Li imide) are reported. The lithium containing mixtures were found to be more than two orders of magnitude more conductive than the parent P₁₂ phase and the 33 mol% Li imide systems showed a solid state conductivity around 1×10⁻⁴ S/cm at 20°C. This solid state conductivity is believed to take place in plastic crystal phases of the P₁₂ compound.

Lithium-ion conducting ceramic/polyether composites

Composites of a lithium ion conducting ceramic with a lithium salt based polymer electrolyte matrix are described. Conductivity measurements as a function of the lithium ion conducting ceramic phase content in the composite show that there is a significant increase in conductivity at approximately 40 vol% of the ceramic. The room temperature conductivity above this ceramic content is enhanced by at least 100% over that of the polymer electrolyte phase alone. It is believed that this additional contribution is substantially lithium ion conduction. The major barrier to ion-motion in these materials appears to be the interface between the polymer and ceramic. This interfacial resistance is strongly moisture-sensitive.