Hexagonal-shaped tin glycolate particles: A preliminary study of their suitability as li-ion insertion electrodes

Tin glycolate particles were prepared by a simple, one-step, polyol-mediated synthesis in air in which tin oxalate precursor was added to ethylene glycol and heated at reflux. Hexagonal-shaped, micron-sized tin glycolate particles were formed when the solution had cooled. A series of tin oxides was produced by calcination of the synthesized tin glycolate at 600-800 degrees C. It was revealed that the micron-sized, hexagonal-shaped tin glycolate now consisted of nanosized tin-based particles (80-120 nm), encapsulated within a tin glycolate shell. XRD, TGA, and FT-IR measurements were conducted to account for the three-dimensional growth of the tin glycolate particles. When applied as an anode material for Li-ion batteries, the synthesized tin glycolate particles showed good electro-chemical reactivity in Li-ion insertion/ deinsertion, retaining a specific capacity of 416mAhg(-1) beyond 50cycles. Ibis performance was significantly better than those of all the other tin oxides nanoparticles (< 160mAhg(-1)) obtained after heat treatment in air. We strongly believe that the buffering of the volume expansion by the glycolate upon Li-Sn alloying is the main factor for the improved cycling of the electrode.

Numerical modeling of the failure mechanisms in Si thin film anode for Li-ion batteries

In recent times, the demand for the storage of electrical energy has grown rapidly for both static applications and the portable electronics enforcing the substantial improvement in battery systems, and Li-ion batteries have been proven to have maximum energy storage density in all rechargeable batteries. However, major breakthroughs are required to consummate the requirement of higher energy density with lower cost to penetrate new markets. Graphite anode having limited capacity has become a bottle neck in the process of developing next generation batteries and can be replaced by higher capacity metals such as Silicon. In the present study we are focusing on the mechanical behavior of the Si-thin film anode under various operating conditions. A numerical model is developed to simulate the intercalation induced stress and the failure mechanism of the complex anode structure. Effect of the various physical phenomena such as diffusion induced stress, plasticity and the crack propagation are investigated to predict better performance parameters for improved design.

Faulted Structures in Li Ion Exchanged NaMO2 (M=Ni(0.25)Mn(0.75))

A family of LiMO2 materials (M=Ni0.25Mn0.75) was prepared from Na1.2-xLixMO∂ precursors (0≤x≤0.6) via ion exchange. The resulting IE products were examined via XRD and compared to simulated XRD patterns produced using DIFFax to determine the defect structures resulting from the IE process. For the 0.1≤x≤0.6 materials, it is observed that there are 3 LiMO2 sub-phases with different Li contents present. As the amount of Li in the precursor increases, the amount of each phase changes resulting in a net shift to higher 2-theta; corresponding to an overall decrease in lattice parameter, approaching the theoretical values for LiMO2. Additionally, as x increases, the probability of O3-type shifting increases, most likely due to an increase in the amount O3-Li2MO3 minority phase which acts to weaken bonds in the TM layer, allowing the O3 shift to occur more easily. For the x=0 IE product, it was seen that the product had an ~O2-type structure, but with lattice parameters closer to those expected for a NaMO2 material.

Li distribution characterization in Li-ion batteries positive electrodes containing LixNi0.8Co0.15Al0.05O2 secondary particles

The elemental distribution of as-received (non-charged) and charged Li-ion battery positive electrodes containing LixNi0.8Co0.15Al0.05O2 (0.75 ? x ? 1.0) microparticles as active material is characterized by combining μ-PIXE and μ-PIGE techniques. PIGE measurements evidence that the Li distribution is inhomogeneous (existence of Li-rich and Li-depleted regions) in as-received electrodes corresponding with the distribution of secondary particles but it is homogeneous within the studied individual secondary micro-particles. The dependence of the Li distribution on electrode thickness and on charging conditions is characterized by measuring the Li distribution maps in specifically fabricated cross-sectional samples. These data show that decreasing the electrode thickness down to 35 μm and charging the batteries at slow rate give rise to more homogeneous Li depth profiles.

Electrochemical characteristics of ordered mesoporous carbon used as electrode material in Li-ion battery

Ordered mesoporous carbon CMK-5 was comprehensively tested for the first time as electrode materials in lithium ion battery. The surface morphology, pore structure and crystal structure were investigated by Scanning Electronic Microscopy (SEM), N-2 adsorption technique and X-ray diffraction (XRD) respectively. Electrochemical properties of CMK-5 were studied by galvanostatic cycling and cyclic voltammetry, and compared with conventional anode material graphite. Results showed that the reversible capacity of CMK-5 was 525 mAh/g at the third charge-discharge cycle and that CMK-5 was more compatible for quick charge-discharge cycling because of its special mesoporous structure. Of special interest was that the CMK-5 gave no peak on its positive sweep of the cyclic voltammetry, which was different from all the other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also applied to investigate the charge-discharge characteristics of CMK-5.

Synthesis of ordered nanoporous carbon and its application in Li-ion battery

Ordered nanoporous carbon (ONC) was comprehensively tested for the first time as electrode material in lithium-ion battery. Structure characterization shows the order nanoporous structure and tiny crystallite structure of as-synthesized ONC. The electrochemical properties of this carbon were studied by galvanostatic cycling and cyclic voltammetry. Of special interest is that ONC gave no peak on its positive sweep of the cyclic voltammetry, which was different from other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also used to investigate the electrochemical characteristics of ONC. (c) 2006 Elsevier Ltd. All rights reserved.

Enhanced 3-dimensional carbon nanotube based anodes for lithium-ion battery applications

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg–1 ). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg–1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg–1 at 0.17C and cycling stability of 130 mAhg –1 up to 50 cycles at 1.7C.

Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.

Assessing charge contribution from thermally treated Ni foam as current collectors for Li-ion batteries

In this report we have investigated the use of Ni foam substrates as anode current collectors for Li-ion batteries. As the majority of reports in the literature focus on hydrothermal formation of materials on Ni foam followed by a high temperature anneal/oxidation step, we probed the fundamental electrochemical responses of as received Ni foam substrates and those subjected to heating at 100°C, 300°C and 450°C. Through cyclic voltammetry and galvanostatic testing, it is shown that the as received and 100°C annealed Ni foam show negligible electrochemical activity. However, Ni foams heated to higher temperature showed substantial electrochemical contributions which may lead to inflated capacities and incorrect interpretations of CV responses for samples subjected to high temperature anneals. XRD, XPS and SEM analyses clearly illustrate that the formation of electrochemically active NiO nanoparticles on the surface of the foam is responsible for this behavior. To further investigate the contribution of the oxidized Ni foam to the overall electrochemical response, we formed Co3O4 nanoflowers directly on Ni foam at 450°C and showed that the resulting electrochemical response was dominated by NiO after the first 10 charge/discharge cycles. This report highlights the importance of assessing current collector activity for active materials grown on transition metal foam current collectors for Li-ion applications.

The structural conversion from α-AgVO3 to β-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO3 nanowires (NWs) and their conversion to tunnel structured β-AgVO3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO3 to β-AgVO3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of β-AgVO3 NWs offers insight into the true β-AgVO3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the β-AgVO3 NWs have a core–shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO3 NWs core material. Electrochemical comparison of α-AgVO3 and β-AgVO3 NWs confirms that β-AgVO3 offers improved electrochemical performance. An ex situ structural characterization of β-AgVO3 NWs after the first galvanostatic discharge and charge offers new insight into the Li+ reaction mechanism for β-AgVO3. Ag+ between the van der Waals layers of the vanadium oxide is reduced during discharge and deposited as metallic Ag, the vacant sites are then occupied by Li+.

Effect of the Electrolyte Formulation on the Performances of Edlc and Li-Ion Batteries

One of the most important components in electrochemical storage devices (batteries and supercapacitors) is undoubtedly the electrolyte. The basic function of any electrolyte in these systems is the transport of ions between the positive and negative electrodes. In addition, electrochemical reactions occurring at each electrode/electrolyte interface are the origin of the current generated by storage devices. In other words, performances (capacity, power, efficiency and energy) of electrochemical storage devices are strongly related to the electrolyte properties, as well as, to the affinity for the electrolyte to selected electrode materials. Indeed, the formulation of electrolyte presenting good properties, such as high ionic conductivity and low viscosity, is then required to enhance the charge transfer reaction at electrode/electrolyte interface (e.g. charge accumulation in the case of Electrochemical Double Layer Capacitor, EDLC). For practical and safety considerations, the formulation of novel electrolytes presenting a low vapor pressure, a large liquid range temperature, a good thermal and chemical stabilities is also required.

This lecture will be focused on the effect of the electrolyte formulation on the performances of electrochemical storage devices (Li-ion batteries and supercapacitors). During which, a summary of the physical, thermal and electrochemical data obtained by our group, recently, on the formulation of novel electrolyte-based on the mixture of an ionic liquid (such as EmimNTf2 and Pyr14NTf2) and carbonate or dinitrile solvents will be presented and commented. The impact of the electrolyte formulation on the storage performances of EDLC and Li-ion batteries will be also discussed to further understand the relationship between electrolyte formulation and electrochemical performances. This talk will also be an opportunity to further discuss around the effects of additives (SEI builder: fluoroethylene carbonate and vinylene carbonate), ionic liquids, structure and nature of lithium salt (LiTFSI vs LiPF6) on the cyclability of negative electrode to then enhance the electrolyte formulation. For that, our recent results on TiSnSb and graphite negative electrodes will be presented and discussed, for example 1,2.

1-C. Marino, A. Darwiche1, N. Dupré, H.A. Wilhelm, B. Lestriez, H. Martinez, R. Dedryvère, W. Zhang, F. Ghamouss, D. Lemordant, L. Monconduit “ Study of the Electrode/Electrolyte Interface on Cycling of a Conversion Type Electrode Material in Li Batteries” J. Phys.chem. C, 2013, 117, 19302-19313

2- Mouad Dahbi, Fouad Ghamouss, Mérièm Anouti, Daniel Lemordant, François Tran-Van “Electrochemical lithiation and compatibility of graphite anode using glutaronitrile/dimethyl carbonate mixtures containing LiTFSI as electrolyte” 2013, 43, 4, 375-385.

Optimization of Li-ion solid electrolytes

The synthesis and optimization of two Li-ion solid electrolytes were studied in this work. Different combinations of precursors were used to prepare La0.5Li0.5TiO3 via mechanosynthesis. Despite the ability to form a perovskite phase by the mechanochemical reaction it was not possible to obtain a pure La0.5Li0.5TiO3 phase by this process. Of all the seven combinations of precursors and conditions tested, the one where La2O3, Li2CO3 and TiO2 were milled for 480min (LaOLiCO-480) showed the best results, with trace impurity phases still being observed. The main impurity phase was that of La2O3 after mechanosynthesis (22.84%) and Li2TiO3 after calcination (4.20%). Two different sol-gel methods were used to substitute boron on the Zr-site of Li1+xZr2-xBx(PO4)3 or the P-site of Li1+6xZr2(P1-xBxO4)3, with the doping being achieved on the Zr-site using a method adapted from Alamo et al (1989). The results show that the Zr-site is the preferential mechanism for B doping of LiZr2(PO4)3 and not the P-site. Rietveld refinement of the unit-cell parameters was performed and it was verified by consideration of Vegard’s law that it is possible to obtain phase purity up to x = 0.05. This corresponds with the phases present in the XRD data, that showed the additional presence of the low temperature (monoclinic) phase for the powder sintered at 1200ºC for 12h of compositions with x ≥ 0.075. The compositions inside the solid solution undergo the phase transition from triclinic (PDF#01-074-2562) to rhombohedral (PDF#01-070-6734) when heating from 25 to 100ºC, as reported in the literature for the base composition. Despite several efforts, it was not possible to obtain dense pellets and with physical integrity after sintering, requiring further work in order to obtain dense pellets for the electrochemical characterisation of Li Zr2(PO4)3 and Li1.05Zr1.95B0.05(PO4)3.

Lightweight metal halide and hydride fast Li ion conductors

This work was motivated by the extensive research on lithium solid state materials, which have attracted increasing interest for potential applications in hydrogen storage and/or lithium ion batteries due to their extraordinary properties. In this thesis, LiBH4-derived materials, LiInBr4 and complex phases based on lithium ammonia borane with potential use as solid state electrolytes were successfully synthesised and characterised.

MEMS SENSOR PLATFORMS FOR IN SITU CHARACTERIZATION OF LI-ION BATTERY ELECTRODES

Lithium-ion batteries provide high energy density while being compact and light-weight and are the most pervasive energy storage technology powering portable electronic devices such as smartphones, laptops, and tablet PCs. Considerable efforts have been made to develop new electrode materials with ever higher capacity, while being able to maintain long cycle life. A key challenge in those efforts has been characterizing and understanding these materials during battery operation. While it is generally accepted that the repeated strain/stress cycles play a role in long-term battery degradation, the detailed mechanisms creating these mechanical effects and the damage they create still remain unclear. Therefore, development of techniques which are capable of capturing in real time the microstructural changes and the associated stress during operation are crucial for unravelling lithium-ion battery degradation mechanisms and further improving lithium-ion battery performance. This dissertation presents the development of two microelectromechanical systems sensor platforms for in situ characterization of stress and microstructural changes in thin film lithium-ion battery electrodes, which can be leveraged as a characterization platform for advancing battery performance. First, a Fabry-Perot microelectromechanical systems sensor based in situ characterization platform is developed which allows simultaneous measurement of microstructural changes using Raman spectroscopy in parallel with qualitative stress changes via optical interferometry. Evolutions in the microstructure creating a Raman shift from 145 cm−1 to 154 cm−1 and stress in the various crystal phases in the LixV2O5 system are observed, including both reversible and irreversible phase transitions. Also, a unique way of controlling electrochemically-driven stress and stress gradient in lithium-ion battery electrodes is demonstrated using the Fabry-Perot microelectromechanical systems sensor integrated with an optical measurement setup. By stacking alternately stressed layers, the average stress in the stacked electrode is greatly reduced by 75% compared to an unmodified electrode. After 2,000 discharge-charge cycles, the stacked electrodes retain only 83% of their maximum capacity while unmodified electrodes retain 91%, illuminating the importance of the stress gradient within the electrode. Second, a buckled membrane microelectromechanical systems sensor is developed to enable in situ characterization of quantitative stress and microstructure evolutions in a V2O5 lithium-ion battery cathode by integrating atomic force microscopy and Raman spectroscopy. Using dual-mode measurements in the voltage range of the voltage range of 2.8V – 3.5V, both the induced stress (~ 40 MPa) and Raman intensity changes due to lithium cycling are observed. Upon lithium insertion, tensile stress in the V2O5 increases gradually until the α- to ε-phase and ε- to δ-phase transitions occur. The Raman intensity change at 148 cm−1 shows that the level of disorder increases during lithium insertion and progressively recovers the V2O5 lattice during lithium extraction. Results are in good agreement with the expected mechanical behavior and disorder change in V2O5, highlighting the potential of microelectromechanical systems as enabling tools for advanced scientific investigations. The work presented here will be eventually utilized for optimization of thin film battery electrode performance by achieving fundamental understanding of how stress and microstructural changes are correlated, which will also provide valuable insight into a battery performance degradation mechanism.