Synthesis, structure and ionic conductivity of La2/3-xLi3xMoO4

A series of compounds, La2/3 - xLi3xMoO4, were first prepared. Their structures are tetragonal scheelites with the cationic defects. The cell parameters a, c and values of c/a decrease with the increasing of the substitution amount (3x) of lithium ion. Cationic vacancies are getting more as Li+ concentration is lower. The diffusion of lithium ion is predominant. The concentration of charge carriers increases with increasing the substitution amount (3x) of lithium ion, meanwhile, the concentration of cationic vacancies decreases. The conductivity approaches the best when the substitution amount (3x) of lithium ion is about 0.3. The conductivity of La0.567Li0.3MoO4 is 6.5 x 10(-6) S . cm(-1) at room temperature.

基于EKF的AMR锂电池SOC动态估计研究

AMR在科研和军事方面的应用决定了其需要一个能够准确、实时估计出锂电池SOC的估计值。由于AMR工作中的放电具有很强的动态性,使得传统估计方法用于锂电池SOC的动态估计效果很不理想。本文描述了EKF方法在AMR锂电池SOC动态估计中的应用。模拟AMR工况进行动态放电试验。试验结果表明,该估计方法能够实时而准确地得到SOC值。

基于UKF滤波的自主移动机器人锂电池SOC估计

准确估计剩余电量(state of charge,SOC)关系到自主移动机器人(AMR)的生存与安全,是AMR研究中所面临的主要挑战之一。针对广义卡尔曼滤波估计SOC的不足,本文给出基于无色卡尔曼滤波(UKF)估计AMR锂电池SOC的新方法。通过试验对UKF和EKF进行了比较。试验验证了同样条件下,UKF比EKF具有更好的滤波估计精度。

Wireless sensor node design for heterogeneous networks

Two complementary wireless sensor nodes for building two-tiered heterogeneous networks are presented. A larger node with a 25 mm by 25 mm size acts as the backbone of the network, and can handle complex data processing. A smaller, cheaper node with a 10 mm by 10 mm size can perform simpler sensor-interfacing tasks. The 25mm node is based on previous work that has been done in the Tyndall National Institute that created a modular wireless sensor node. In this work, a new 25mm module is developed operating in the 433/868 MHz frequency bands, with a range of 3.8 km. The 10mm node is highly miniaturised, while retaining a high level of modularity. It has been designed to support very energy efficient operation for applications with low duty cycles, with a sleep current of 3.3 μA. Both nodes use commercially available components and have low manufacturing costs to allow the construction of large networks. In addition, interface boards for communicating with nodes have been developed for both the 25mm and 10mm nodes. These interface boards provide a USB connection, and support recharging of a Li-ion battery from the USB power supply. This paper discusses the design goals, the design methods, and the resulting implementation.

3D vanadium oxide inverse opal growth by electrodeposition

Three-dimensional vanadium pentoxide (V2O5) material architectures in the form of inverse opals (IOs) were fabricated using a simple electrodeposition process into artificial opal templates on stainless steel foil using an aqueous solution of VOSO4.χH2O with added ethanol. The direct deposition of V2O5 IOs was compared with V2O5 planar electrodeposition and confirms a similar progressive nucleation and growth mechanism. An in-depth examination of the chemical and morphological nature of the IO material was performed using X-ray crystallography, X-ray photoelectron spectroscopy, Raman scattering and scanning/transmission electron microscopy. Electrodeposition is demonstrated to be a function of the interstitial void fraction of the artificial opal and ionic diffusivity that leads to high quality, phase pure V2O5 inverse opals is not adversely affected by diffusion pathway tortuosity. Methods to alleviate electrodeposited overlayer formation on the artificial opal templates for the fabrication of the porous 3D structures are also demonstrated. Such a 3D material is ideally suited as a cathode for lithium ion batteries, electrochromic devices, sensors and for applications requiring high surface area electrochemically active metal oxides.

An effective three-dimensional ordered mesoporous ZnCo2O4 as electrocatalyst for Li-O2 batteries

Three-dimensional ordered mesoporous (3DOM) ZnCo₂O₄ materials have been synthesized via a hard template and used as bifunctional electrocatalysts for rechargeable Li-O₂ batteries. The as-prepared ZnCo₂O₄ nanoparticles possess a high specific surface area of 127.2 m² g^-1 and a spinel crystalline structure. The Li-O₂ battery utilizing 3DOM ZnCo₂O₄ shows a higher specific capacity of 6024 mAh g^-1 than that with pure Ketjen black (KB). Moreover, the ZnCo₂O₄-based electrode enables much enhanced cyclability with a smaller discharge-recharge voltage gap than that of the carbon-only cathode. Such excellent catalytic performance of ZnCo₂O₄ could be associated with its larger surface area and 3D ordered mesoporous structure

The Influence of Cation Structure on the Chemical-Physical Properties of Protic Ionic Liquids

In this study we investigated the influence of five different cations on the physical-chemical properties of protic ionic liquids (PILs) based on bis(trifluoromethanesulfonyl)imide (TFSI-). We showed that the viscosities, ionic conductivities, densities and thermal properties of these PIL are strongly affected by the structure of the protic cation. Furthermore, the influence of the cation structure on the lithium coordination was investigated by Raman spectroscopy for all investigated PIL-based electrolytes for lithium-ion batteries (LIBs). This investigation clearly demonstrates, that the lithium average coordination number in PIL-based electrolytes is strongly affected by (ring) size and the number of protons on the cations structure and, more importantly, it might be significantly lower (more than 60 of that of electrolytes containing aprotic ionic liquids (AILs). Electrochemical performances of these PILs-based electrolytes were then also investigated to dress some conclusion on their applicability for LIB.

Determination of the thermal parameters of high-power batteries by local heat

A new approach to the determination of the thermal parameters of high-power batteries is introduced here. Application of local heat flux measurement with a gradient heat flux sensor (GHFS) allows determination of the cell thermal parameters in di_erent surface points of the cell. The suggested methodology is not cell destructive as it does not require deep discharge of the cell or application of any charge/discharge cycles during measurements of the thermal parameters of the cell. The complete procedure is demonstrated on a high-power Li-ion pouch cell, and it is verified on a sample with well-known thermal parameters. A comparison of the experimental results with conventional thermal characterization methods shows an acceptably low error. The dependence of the cell thermal parameters on state of charge (SoC) and measurement points on the surface was studied by the proposed measurement approach.

Synthèse du LiXFePO4 par voie fondue et l’étude de la couche de carbone sur LiFePO4

Le LiFePO4 est un matériau prometteur pour les cathodes des batteries au lithium. Il possède une bonne stabilité à haute température et les précurseurs utilisés pour la synthèse sont peu couteux. Malheureusement, sa faible conductivité nuit aux performances électrochimiques. Le fait de diminuer la taille des particules ou d’enrober les particules d’une couche de carbone permet d’augmenter la conductivité. Nous avons utilisé une nouvelle méthode appelée « synthèse par voie fondue » pour synthétiser le LiFePO4. Cette synthèse donne des gros cristaux et aucune impureté n’est détectée par analyse Rayon-X. En revanche, la synthèse de LiXFePO4 donne un mélange de LiFePO4 pur et d’impureté à base de lithium ou de fer selon l’excès de fer ou de lithium utilisé. La taille des particules de LiFePO4 est réduite à l’aide d’un broyeur planétaire et plusieurs paramètres de broyage sont étudiés. Une couche de carbone est ensuite déposée sur la surface des particules broyées par un traitement thermique sur le LiFePO4 avec du -lactose. L’influence de plusieurs paramètres comme la température du traitement thermique ou la durée du chauffage sont étudiés. Ces expériences sont réalisées avec un appareil d’analyse thermogravimétrique (ATG) qui donne la quantité de chaleur ainsi que la variation de masse durant le chauffage de l’échantillon. Ce nouveau chauffage pour la couche de carbone donne des échantillons dont les performances électrochimiques sont similaires à celles obtenues précédemment avec la méthode de chauffage pour la couche de carbone utilisant le four tubulaire.

Structural transformation of graphite by arc-discharge

The formation of novel structures by the passage of an electric current through graphite is described. These structures apparently consist of hollow three-dimensional graphitic shells bounded by curved and faceted planes, typically made up of two graphene layers. The curved structures were frequently decorated with nano-scale carbon particles, or short nanotubes. In some cases, nanotubes were found to be seamlessly connected to the thin shells, indicating that the formation of the shells and the nanotubes is intimately connected. Small nanotubes or nanoparticles were also sometimes found encapsulated inside the hollow structures, while fullerene-like particles were often seen attached to the outside surfaces. With their high surface areas and structural perfection, the new carbon structures may have applications as anodes of lithium ion batteries or as components of composite materials.

Transport properties of ionic liquid electrolytes with organic diluents

Ionic liquids (ILs) form a novel class of electrolytes with unique properties that make them attractive candidates for electrochemical devices. In the present study a range of electrolytes were prepared based on the IL N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]) and LiNTf2 salt. The traditional organic solvent diluents vinylene carbonate (VC), ethylene carbonate (EC), tetrahydrofuran (THF) and toluene were used as additives at two concentrations, 10 and 20 mol%, leading to a ratio of about 0.6 and 1.3 diluent molecules to lithium ions, respectively. Most promisingly, the lithium ions see the greatest effect in the presence of all the diluents, except toluene, producing a lithium self-diffusion coefficient of almost a factor of 2.5 times greater for THF at 20 mol%. Raman spectroscopy subtly indicates that THF may be effectively breaking up a small portion of the lithium ion–anion interaction. While comparing the measured molar conductivity to that calculated from the self-diffusion coefficients of the constituents indicates that the diluents cause an increase in the overall ion clustering. This study importantly highlights that selective ion transport enhancement is achievable in these materials.

Characterisation and impedance spectroscopy of substituted Li1.3Al0.3Ti1.7(PO4)3−x(ZO4)x (Z=V, Nb) ceramics*1

Lithium ion conducting ceramics based on the lithium aluminium titanium phosphate (LATP) NASICON structure have been prepared with various substitutions of the phosphorous. The effect of the processing method has been shown to be the key factor in determining the conductivity, both bulk and grain boundary, as well as the conductivity trends observed as a function of substitution.

Compositional effects on structure and transport properties in a polyelectrolyte gel

The copolymerization of lithium 2-acrylamido-2-methyl-1-propane sulfonate (LiAMPS) with N,N ′-dimethylacrylamide has yielded polyelectrolyte systems which can be gelled with an ethylene carbonate/N ′,N ′-dimethylacetamide solvent mixture and show high ionic conductivities. 7Li linewidth and relaxation times as well as 1H NMR diffusion coefficients have been used to investigate the effect of copolymer composition as well as copolymer concentration in the gel electrolyte with respect to ionic transport and polyelectrolyte structure. It appears that ion association is likely even in the case of low lithium salt concentration; however a rapid exchange exists between the associated and non-associated lithium species. Beyond 0.2 M of LiAMPS, both the conductivity and solvent diffusion reach a plateau, whilst lithium ion linewidth and spin-spin relaxation are suggestive, on average, of a less mobile species. The thermal analysis data is also supportive of this association effectively leading to a form of phase separation on the nanoscale, which gives a lower overall activity of lithium ions in the solvent rich regions beyond about 0.2 M of LiAMPS, thereby leading to an increase in the final liquidus temperature of the binary liquid solvent from –9 to +5°C.

The effect of nano-particle TiO2 fillers on structure and transport in polymer electrolytes

Nano-particle oxide fillers including TiO₂, SiO₂ and Al₂O₃ have previously been shown to have a significant affect on the properties of polymer electrolytes, especially those based on polyether–lithium salt systems. In some cases, conductivity increases of more than one order of magnitude have been reported in crystalline PEO-based complexes. In this work, we report on the effects of TiO₂ on a completely amorphous polyether-based system to remove the complication of multiple phases presented by the semi-crystalline nature of PEO. Multinuclear magnetic resonance spectroscopy has shown that the lithium ion environment is changed by the addition of filler. Vibrational spectroscopy shows that the filler influences the disordered-longitudinal acoustic modes (DLAM) in the case of an amorphous polyether and suggests an interaction between the filler surface and the polymer. Positron annihilation lifetime spectroscopy indicates an increase in free volume upon addition of filler to an amorphous polyether–salt complex, coinciding with an apparent increase in polymer mobility as determined from ¹H T₂ NMR measurements. Impedance spectroscopy has shown clear evidence of an inter-phase region that may be more or less conductive than the bulk polymer electrolyte itself. The data support a model which includes conduction through an interfacial region in addition to the bulk polymer

Organic ionic plastic crystals : recent advances

Investigations into the synthesis and utilisation of organic ionic plastic crystals have made significant progress in recent years, driven by a continued need for high conductivity solid state electrolytes for a range of electrochemical devices. There are a number of different aspects to research in this area; fundamental studies, utilising a wide range of analytical techniques, of both pure and doped plastic crystals, and the development of plastic crystal-based materials as electrolytes in, for example, lithium ion batteries. Progress in these areas is highlighted and the development of new organic ionic plastic crystals, including a new class of proton conductors, is discussed.