Synthèse de titanates de lithium nanostructurés par plasma inductif pour les batteries lithium-ion

Le marché des accumulateurs lithium-ion est en expansion. Cette croissance repose partiellement sur la multiplication des niches d’utilisation et l’amélioration constante de leurs performances. En raison de leur durabilité exceptionnelle, de leur faible coût, de leur haute densité de puissance et de leur fiabilité, les anodes basées sur les titanates de lithium, et plus particulièrement le spinelle Li4Ti5O12, présentent une alternative d’intérêt aux matériaux classiques d’anodes en carbone pour de multiples applications. Leur utilisation sous forme de nanomatériaux permet d’augmenter significativement la puissance disponible par unité de poids. Ces nanomatériaux ne sont typiquement pas contraints dans une direction particulière (nanofils, nanoplaquettes), car ces formes impliquent une tension de surface plus importante et requièrent donc généralement un mécanisme de synthèse dédié. Or, ces nanostructures permettent des réductions supplémentaires dans les dimensions caractéristiques de diffusion et de conduction, maximisant ainsi la puissance disponible, tout en affectant les propriétés habituellement intrinsèques des matériaux. Par ailleurs, les réacteurs continus reposant sur la technologie du plasma thermique inductif constituent une voie de synthèse démontrée afin de générer des volumes importants de matériaux nanostructurés. Il s’avère donc pertinent d’évaluer leur potentiel dans la production de titanates de lithium nanostructurés. La pureté des titanates de lithium est difficile à jauger. Les techniques de quantification habituelles reposent sur la fluorescence ou la diffraction en rayons X, auxquelles le lithium élémentaire se prête peu ou pas. Afin de quantifier les nombreuses phases (Li4Ti5O12, Li2Ti3O7, Li2TiO3, TiO2, Li2CO3) identifiées dans les échantillons produits par plasma, un raffinement de Rietveld fut développé et validé. La présence de γ-Li2TiO3 fut identifiée, et la calorimétrie en balayage différentiel fut explorée comme outil permettant d’identifier et de quantifier la présence de β-Li2TiO3. Différentes proportions entre les phases produites et différents types de morphologies furent observés en fonction des conditions d’opération du plasma. Ainsi, des conditions de trempe réductrice et d’ensemencement en Li4Ti5O12 nanométrique semblent favoriser l’émergence de nanomorphologies en nanofils (associés à Li4Ti5O12) et en nanoplaquette (associées à Li2TiO3). De plus, l’ensemencement et les recuits augmentèrent significativement le rendement en la phase spinelle Li4Ti5O12 recherchée. Les recuits sur les poudres synthétisées par plasma indiquèrent que la décomposition du Li2Ti3O7 produit du Li4Ti5O12, du Li2TiO3 et du TiO2 (rutile). Afin d’approfondir l’investigation de ces réactions de décomposition, les paramètres cristallins du Li2Ti3O7 et du γ-Li2TiO3 furent définis à haute température. Des mesures continues en diffraction en rayon X à haute température furent réalisées lors de recuits de poudres synthétisées par plasma, ainsi que sur des mélanges de TiO2 anatase et de Li2CO3. Celles-ci indiquent la production d’un intermédiaire Li2Ti3O7 à partir de l’anatase et du carbonate, sa décomposition en Li4Ti5O12 et TiO2 (rutile) sur toute la plage de température étudiée, et en Li2TiO3 et TiO2 (rutile) à des températures inférieures à 700°C.

Synthesis of a porous sheet-like V₂O₅-CNT nanocomposite using an ice-templating 'bricks-and-mortar' assembly approach as a high-capacity, long cyclelife cathode material for lithium-ion batteries

Tailoring the nanostructures of electrode materials is an effective way to enhance their electrochemical performance for energy storage. Herein, an ice-templating "bricks-and-mortar" assembly approach is reported to make ribbon-like V2O5 nanoparticles and CNTs integrated into a two-dimensional (2D) porous sheet-like V2O5-CNT nanocomposite. The obtained sheet-like V2O5-CNT nanocomposite possesses unique structural characteristics, including a hierarchical porous structure, 2D morphology, large specific surface area and internal conducting networks, which lead to superior electrochemical performances in terms of long-term cyclability and significantly enhanced rate capability when used as a cathode material for LIBs. The sheet-like V2O5-CNT nanocomposite can charge/discharge at high rates of 5C, 10C and 20C, with discharge capacities of approximately 240 mA h g-1, 180 mA h g-1, and 160 mA h g-1, respectively. It also retains 71% of the initial discharge capacity after 300 cycles at a high rate of 5C, with only 0.097% capacity loss per cycle. The rate capability and cycling performance of the sheet-like V2O5-CNT nanocomposite are significantly better than those of commercial V2O5 and most of the reported V2O5 nanocomposite.

In situ prepared V2O5/graphene hybrid as a superior cathode material for lithium-ion batteries

Developing synthetic methods for graphene based cathode materials, with low cost and in an environmentally friendly way, is necessary for industrial production. Although the precursor of graphene is abundant on the earth, the most common precursor of graphene is graphene oxide (GO), and it needs many steps and reagents for transformation to graphite. The traditional approach for the synthesis of GO needs many chemicals, thus leading to a high cost for production and potentially great amounts of damage to the environment. In this study, we develop a simple wet ball-milling method to construct a V2O5/graphene hybrid structure in which nanometre-sized V2O5 particles/aggregates are well embedded and uniformly dispersed into the crumpled and flexible graphene sheets generated by in situ conversion of bulk graphite. The combination of V2O5 nanoparticles/aggregates and in situ graphene leads the hybrid to exhibit a markedly enhanced discharge capacity, excellent rate capability, and good cycling stability. This study suggests that nanostructured metal oxide electrodes integrated with graphene can address the poor cycling issues of electrode materials that suffer from low electronic and ionic conductivities. This simple wet ball-milling method can potentially be used to prepare various graphene based hybrid electrodes for large scale energy storage applications.

Disordered spinel LiNi0.5Mn1.5O4 cathode with improved rate performance for lithium-ion batteries

The high voltage LiNi0.5Mn1.5O4 cathode with a disordered spinel structure is synthesized by a glycine-assisted low-temperature reaction follows by a thermal treatment at 750 °C, 850 °C, and 950 °C for 12 h. Glycine is used as a chelating agent for the first time to build required environment for shaping the precursor of LiNi0.5Mn1.5O4 materials. The microstructure and morphology of the LiNi0.5Mn1.5O4 product are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller, and transmission electron microscopy. The sample prepares at 750 °C reveals small particles with well-defined crystals as confirmed by electron microscopy. Electrochemical results demonstrate that LiNi0.5Mn1.5O4 electrode anneal at 750 °C (compare to other two samples) delivers the highest reversible capacity of 110 mAh g-1 at 0.2C after 100 cycles with good rate capability. The enhanced electrochemical performance could be attributed to the smaller particle sizes as well as well-defined crystals which provide a directional and shorter diffusion path length for Li+ transportation within the crystals.

Unexpected effect of tetraglyme plasticizer on lithium ion dynamics in PAMPS based ionomers

Li(+) cation conducting ionomers based on poly(2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) incorporating a low molecular weight plasticizer have been characterized. Previously we have observed an apparent decoupling of ionic conductivity and lithium ion dynamics from the Tg of this ionomer along with an increase in ionic conductivity obtained by incorporating a quaternary ammonium co-cation. The incorporation of tetraglyme as a coordinating plasticizer was investigated in order to further improve the ion dissociation and dynamics. Solid-state NMR, thermal analysis, impedance spectroscopy and infrared spectroscopy were used to characterize these systems. As expected, the glass transition temperature Tg decreased upon the addition of the plasticizer. However, in contrast to the previously reported Na-conducting systems, the ionic conductivity was also decreased by several orders of magnitude, indicating that the tetraglyme recouples the conductivity back to the polymer dynamics. Temperature dependent (7)Li NMR line width and T1 measurements were used to probe the Li(+) dynamics, which were found to be dependent on the Li(+) concentration, the nature of the co-cation and the presence or absence of tetraglyme.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Enhanced 3-Dimensional Carbon Nanotube Based Anodes for Li-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.

One-step preparation of graphene nanosheets via ball milling of graphite and the application in lithium-ion batteries

An improved method for mass production of good-quality graphene nanosheets (GNs) via ball milling pristine graphite with dry ice is presented. We also report the enhanced performance of these GNs as working electrode in lithium-ion batteries (LIBs). In this improved method, the decrease of necessary ball milling time from 48 to 24 h and the increase of Brunauer–Emmett–Teller surface area from 389.4 to 490 m2/g might be resulted from the proper mixing of stainless steel balls with different diameters and the optimization of agitation speed. The as-prepared GNs are investigated in detail using a number of techniques, such as scanning electron microscope, atomic force microscope, high-resolution transmission electron microscopy, selected area electron diffraction, X-ray diffractometer, and Fourier transform infrared spectroscopic. To demonstrate the potential applications of these GNs, the performances of the LIBs with pure Fe3O4 electrode and Fe3O4/graphene (Fe3O4/G) composite electrode were carefully evaluated. Compared to Fe3O4-LIBs, Fe3O4/G-LIBs exhibited prominently enhanced performance and a reversible specific capacity of 900 mAh g−1 after 5 cycles at 100 and 490 mAh g−1 after 5 cycles at 800 mA g−1. The improved cyclic stability and enhanced rate capability were also obtained.

Improved adhesion of active electrode materials to metal electrode substrates

A battery electrode for a lithium ion battery comprising an elec. conductive substrate having an electrode layer applied thereto, characterized in that the electrode layer includes an org. material having high alky., or an org. material which can be dissolved in org. solvents, or an org. material having an imide group(s) and aminoacetal group(s), or an org. material that chelates with or bonds with a metal substrate or that chelates with or bonds with an active material in the electrode layer. The org. material may be guanidine carbonate. [on SciFinder(R)]

A low-power, low-cost soil-moisture sensor using dual-probe heat-pulse technique

This paper presents the development and testing of an integrated low-power and low-cost dual-probe heat-pulse (DPHP) soil-moisture sensor in view of the electrical power consumed and affordability in developing countries. A DPHP sensor has two probes: a heater and a temperature sensor probe spaced 3 mm apart from the heater probe. Supply voltage of 3.3V is given to the heater-coil having resistance of 33 Omega power consumption of 330 mW, which is among the lowest in this category of sensors. The heater probe is 40 mm long with 2 mm diameter and hence is stiff enough to be inserted into the soil. The parametric finite element simulation study was performed to ensure that the maximum temperature rise is between 1 degrees C and 5 degrees C for wet and dry soils, respectively. The discrepancy between the simulation and experiment is less than 3.2%. The sensor was validated with white clay and tested with red soil samples to detect volumetric water-content ranging from 0% to 30%. The sensor element is integrated with low-power electronics for amplifying the output from thermocouple sensor and TelosB mote for wireless communication. A 3.7V lithium ion battery with capacity of 1150 mAh is used to power the system. The battery is charged by a 6V and 300 mA solar cell array. Readings were taken in 30 min intervals. The life-time of DPHP sensor node is around 3.6 days. The sensor, encased in 30 mm x 20 mm x 10 mm sized box, and integrated with electronics was tested independently in two separate laboratories for validating as well as investigating the dependence of the measurement of soil-moisture on the density of the soil. The difference in the readings while repeating the experiments was found out to be less than 0.01%. Furthermore, the effect of ambient temperature on the measurement of soil-moisture is studied experimentally and computationally. (C) 2015 Elsevier B.V. All rights reserved.

Real-Time Stress Measurements in Germanium Thin Film Electrodes during Electrochemical Lithiation/Delithiation Cycling

An in situ study of stress evolution and mechanical behavior of germanium as a lithium-ion battery electrode material is presented. Thin films of germanium are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M LiPF6 in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Real-time stress evolution in the germanium thin-film electrodes during electrochemical lithiation/delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. Upon lithiation a-Ge undergoes extensive plastic deformation, with a peak compressive stress reaching as high as -0.76 +/- 0.05 GPa (mean +/- standard deviation). The compressive stress decreases with lithium concentration reaching a value of approximately -0.3 GPa at the end of lithiation. Upon delithiation the stress quickly became tensile and follows a trend that mirrors the behavior on compressive side; the average peak tensile stress of the lithiated Ge samples was approximately 0.83 GPa. The peak tensile stress data along with the SEM analysis was used to estimate a lower bound fracture resistance of lithiated Ge, which is approximately 5.3 J/m(2). It was also observed that the lithiated Ge is rate sensitive, i.e., stress depends on how fast or slow the charging is carried out. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.

利用重离子辐照及蚀刻技术制备锂离子电池隔膜

本文通过对目前锂离子电池市场及锂离子电池隔膜制备现状的研究，提出采用重离子辐照技术制备锂离子电池隔膜的新方法。拓展了重离子辐照技术的应用，为锂离子电池隔膜的国产化另辟蹊径。实验中，用能量25 MeV/u 的Kr86及11.4 MeV/u的197Au离子，以1×108 cm-2-5×109 cm-2剂量辐照聚丙烯薄膜，通过电导测量法监测蚀刻液的参数，包括温度、硫酸浓度、重铬酸钾浓度对径迹蚀刻速率的影响，得到适合的蚀刻条件；并用场发射扫描电镜对孔的形状及孔径大小进行表征；成功制备出孔径均匀、具有密度和大小可控的重离子径迹聚丙烯孔膜；对孔洞锥角的形成进行分析，给出锥角的计算公式，为利用重离子辐照技术制备锂离子电池隔膜提供了实验数据