1,721,041 research outputs found
A high-power and fast charging Li-ion battery with outstanding cycle-life
No full textElectrochemical energy storage devices based on Li-ion cells currently power almost all electronic devices and power tools. The development of new Li-ion cell configurations by incorporating innovative functional components (electrode materials and electrolyte formulations) will allow to bring this technology beyond mobile electronics and to boost performance largely beyond the state-of-the-art. Here we demonstrate a new full Li-ion cell constituted by a high-potential cathode material, i.e. LiNi0.5Mn1.5O4, a safe nanostructured anode material, i.e. TiO2, and a composite electrolyte made by a mixture of an ionic liquid suitable for high potential applications, i.e. Pyr1,4PF6, a lithium salt, i.e. LiPF6, and standard organic carbonates. The final cell configuration is able to reversibly cycle lithium for thousands of cycles at 1000 mAg-1 and a capacity retention of 65% at cycle 2000. © 2017 The Author(s)
H2 thermal desorption and hydride conversion reactions in Li cells of TiH2/C amorphous nanocomposites
No full textHere we investigate the properties of amorphous TiH2/carbon nanocomposites as possible active material in lithium cells. Several TiH2/C mixtures are prepared by a mechanochemical route, by varying the carbon/hydride ratio. Materials are tested in electrochemical cells versus lithium metal in EC:DMC LiPF6 electrolyte by galvanostatic cycling (GC) and are characterized by X-ray diffraction, transmission electron microscopy, thermogravimetry and mass spectrometry. Thermal dehydrogenation processes are altered by the mechanochemical treatment of the sample: milling decreases the hydrogen content of the hydride. On the other hand, the mechanochemical grinding increases the specific capacity delivered during the first GC discharge. We suggest that the electrochemical process is the result of a delicate balance between the absolute quantity of hydrogen and its availability for the hydride conversion reaction. © 2015 Elsevier B.V
Origin of the Voltage Hysteresis of MgH2 Electrodes in Lithium Batteries
No full textMagnesium hydride has been proposed as innovative anode material for Li ion cells due to its large theoretical capacity and high-energy efficiency compared to other conversion materials. In this work, we report a combined experimental-theoretical study about the origin of voltage hysteresis in the conversion reaction of MgH2 in lithium cells. Experimentally, the extent of the thermodynamic voltage hysteresis in the first galvanostatic discharge-charge cycle has been determined by the GITT technique and decoupled from the kinetic overpotentials. Theoretically, the origin of the thermodynamic voltage hysteresis has been evaluated and studied by means density functional theory calculations within the supercell approach. Different elementary reactions have been modeled upon reduction and oxidation on the surfaces of the active phases (i.e., MgH2, LiH, and Mg), and the associated theoretical voltages have been predicted. Experimental and theoretical results have been compared and discussed to draw a comprehensive description of the elementary surface reactions of the MgH2 conversion in lithium cells. © 2015 American Chemical Society
Lightweight borohydrides electro-activity in lithium cells
No full textAs a substitute for graphite, the negative electrode material commonly used in Li-ion batteries, hydrides have the theoretical potential to overcome performance limits of the current state-of-the-art Li-ion cells. Hydrides can operate through a conversion process proved for some interstitial hydrides like MgH2: MxAy+ n Li = x M + y LimA, where m = n/y. Even if far from optimization, outstanding performances were observed, drawing the attention to the whole hydride family. Looking for high capacity systems, lightweight complex metal hydrides, such as borohydrides, deserve consideration. Capacities in the order of 2000-4000 mAh/g can be theoretically expected thanks to the very low formula unit weight. Although the potential technological impact of these materials can lead to major breakthroughs in Li-ion batteries, this new research field requires the tackling of fundamental issues that are completely unexplored. Here, our recent findings on the incorporation of borohydrides are presented and discussed. © 2016 by the authors
Magnesium hydride as negative electrode active material in lithium cells: A review
No full textMgH2 has been recently proposed in 2008 as novel conversion material for negative electrodes in lithium ion cells (LIC). Since then, many aspects of the electrochemical behaviour in LIC of this material have been investigated: both experimental and computational studies have been carried out to investigate the fundaments of the MgH2 conversion reaction and to demonstrate performances in LIC close to the theoretical predictions (2037 mAh g−1 and 2842 mAh cm−3). The conversion process involves a reversible redox reaction where the pristine binary hydride is electrochemically reduced to magnesium nanoparticles surrounded by a LiH matrix, and oxidized back to MgH2. In recent years the research efforts on this material have been focused on: (a) the identification of successful synthetic routes to achieve good performances in LIC; (b) the understanding of the basics of the MgH2 conversion reaction; (c) the optimization of technological aspects to improve the performances in LIC (e.g. electrode formulation assessment and adoption of solid electrolytes). In this paper we present a comprehensive review about the research studies reported in the literature concerning the use of MgH2 as negative electrode for lithium ion cells. © 2017 Elsevier Lt
A mixed mechanochemical-ceramic solid-state synthesis as simple and cost effective route to high-performance LiNi0.5Mn1.5O4 spinels.
No full textThe implementation of high potential materials as positive electrodes in high energy Li-ion batteries requires to develop scalable and smart synthetic routes. In the case of the LiNi0.5Mn1.5O4 (LNMO) spinel material, a successful preparation strategy must drive the phase formation in order to obtain structural, morphological and surface properties capable to boost performances in lithium cells and minimize the electrolyte degradation. Here we discuss a novel simple and easily scalable mechanochemical synthetic route, followed by a high temperature annealing in air, to prepare LMNO materials starting from oxides. A synergic doping with chromium and iron has been incorporated, resulting in the spontaneous segregation of a CrOx-rich surface layer. The effect of the annealing temperature on the physico-chemical properties of the LMNO material has been investigated as well as the effect on the performances in Li-cells. © 2017 Elsevier Lt
Reactivity of Sodium Alanates in Lithium Batteries
No full textNovel chemistries for secondary batteries are investigated worldwide in order to boost the development of next-generation rechargeable storage systems and especially of lithium-devices. High capacity anode materials for Li-ion cells are at the center stage of R&D in order to improve the performances. In this view, conversion materials are an exciting playground. Among the various proposed class of conversion anodes, metal hydrides are probably the most challenging and promising due to the high theoretical capacities, instability toward the standard carbonate-based electrolytes, large volume variations upon cycling, and moderately low working voltages. Among them lightweight hydrides, like alkaline alanates, are an almost unexplored family of materials. In this study, we present a fundamental study on the electrochemical conversion reaction of sodium alanates: NaAlH4, Na3AlH6, and Na2LiAlH6. Our goal is to improve the understanding of the basic solid-state electrochemistry that drives the conversion reactions of these materials in lithium cells. Samples have been prepared mechanochemically and characterized by X-ray diffraction (XRD), infrared spectroscopy, and transmission electron microscopy. All materials have been assembled in lithium cells with a commercial liquid electrolyte to test their electrochemical activity. The Li incorporation/deincorporation mechanism for all materials has been explored by in situ XRD and interpreted also in view of density functional theory thermodynamic calculations. © 2015 American Chemical Society
Investigation of the effects of mechanochemical treatment on NaAlH4 based anode materials for Li-ion batteries
No full textSodium alanate has proven to be a feasible candidate for electrochemical applications. Within a lithium cell, NaAlH4 closely approaches its theoretical capacity of 1985 mAhg-1 upon the first discharge. Despite its high specific capacity, NaAlH4 suffers from poor cycle efficiency, mostly due to the severe volume expansion following the conversion reaction and resulting in damage to electrode mechanical integrity with loss of electrical contact. Synthesis of an appropriate composite alanate/carbon by high energy ball milling demonstrates an ability to mitigate these deleterious effects, whereby large improvements in terms of electrochemical reversibility can be achieved. In order to highlight the effects of mechanochemical treatment on the electrochemical properties of NaAlH4, new insights on such NaAlH4/C composites are reported. Solid state NMR has been used to study the impact of ball milling on the NaAlH4 crystal structure, while, the hydrogen content and associated desorption properties have been evaluated by thermal programmed desorption measurements. Also, electrochemical features have been analyzed via the combined application of potentiodynamic cycling with galvanostatic acceleration and electrochemical impedance spectroscopy measurements. Finally, new evidence concerning the reversibility of the conversion processes has been obtained by ex-situ NMR measurements on cycled electrodes. © 2016 The Electrochemical Society. All rights reserved
Extremely pure Mg2FeH6 as a negative electrode for lithium batteries
No full textNanocrystalline samples of Mg-Fe-H were synthesized by mixing of MgH2 and Fe in a 2:1 molar ratio by hand grinding (MIX) or by reactive ball milling (RBM) in a high-pressure vial. Hydrogenation procedures were performed at various temperatures in order to promote the full conversion to Mg2FeH6. Pure Mg2FeH6 was obtained only for the RBM material cycled at 485°C. This extremely pure Mg2FeH6 sample was investigated as an anode for lithium batteries. The reversible electrochemical lithium incorporation and de-incorporation reactions were analyzed in view of thermodynamic evaluations, potentiodynamic cycling with galvanostatic acceleration (PCGA), and ex situ X-ray Diffraction (XRD) tests. The Mg2FeH6 phase underwent a conversion reaction; the Mg metal produced in this reaction was alloyed upon further reduction. The back conversion reaction in a lithium cell was here demonstrated for the first time in a stoichiometric extremely pure Mg2FeH6 phase: the reversibility of the overall conversion process was only partial with an overall coulombic yield of 17% under quasi-thermodynamic control. Ex situ XRD analysis highlighted that the material after a full discharge/charge in a lithium cell was strongly amorphized. Under galvanostatic cycling at C/20, C/5 and 1 C, the Mg2FeH6 electrodes were able to supply a reversible capacity with increasing coulombic efficiency and decreasing specific capacity as the current rate increased. © 2018 by the authors
NaAlH4 nanoconfinement in a mesoporous carbon for application in lithium ion batteries
No full textAlanates have recently attracted attention as new anodic materials for lithium ion batteries. The electrochemical activity of sodium alanate has been already reported and the conversion mechanism explained. Through a complex conversion reaction, this compound is able to develop almost all the theoretical capacity, achieving more than 1700 mAh/g upon first discharge with an efficiency of 70%. Nevertheless alanate undergoes to capacity fade in few cycles. This is mainly due to the severe structural reorganization following the conversion reaction, that results in electrode pulverization and loss of electric contact. Here, we present a nanocomposite material consisting of NaAlH4 confined in the nanoporous of a carbon matrix able to mitigate the effect of volume expansion and improve the cyclability. Specifically, the nanocomposite has been studied in terms of structure, morphology and hydrogen content by the means of Infrared Spectroscopy, solid state NMR, electronic microscopy and thermal analysis. Finally, its performance in lithium cells is presented. © 2017 The Electrochemical Society. All rights reserved
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