Thermal stability analysis of nitrile additives in LiFSI for lithium-ion batteries: An accelerating rate calorimetry study.

Although lithium-ion batteries (LIBs) are extensively used as secondary storage energy devices, they also pose a significant fire and explosion hazard. Subsequently, thermal stability studies for LiPF6- and LiFSI-type electrolytes have been conducted extensively. However, the thermal characteristics of these electrolytes with thermally stable additives in a full cell assembly have yet to be explored. This study presents a comprehensive accelerating rate calorimetry (ARC) study. First, 1.2-Ah cells were prepared using a control commercial LiPF6 electrolyte and LiFSI with a specific succinonitrile additive and ethyl-methyl carbonate as a thermally stable electrolyte additive. The kinetic parameters involved in heat generation and their effects on the thermal properties of the ARC module were analyzed from the heat-wait-seek (HWS), self-heating (SH), and thermal runaway (TR) stages. The results indicate that the addition of a succinonitrile additive to the LiFSI electrolyte lowers the decomposition temperatures of the solid electrolyte interface (SEI) owing to polymerization with Li at the anode, while simultaneously increasing the activation energy of reaction temperatures at SEI between the separator and the electrolyte. The maximum thermal-runaway temperature decreased from 417 °C (ΔH = 5.26 kJ) (LiPF6) to 285 °C (ΔH = 2.068 kJ) (LiFSI + succinonitrile). This study provides key insights to the thermal characteristics of LiPF6 and LiFSI during the self-heating and thermal runaway stages and indicates a practical method for achieving thermally stable LIBs.

Anodic WO3 mesosponge @ carbon: a novel binder-less electrode for advanced energy storage devices.

A novel design for an anodic WO3 mesosponge @ carbon has been introduced as a highly stable and long cyclic life Li-ion battery electrode. The nanocomposite was successfully synthesized via single-step electrochemical anodization and subsequent heat treatment in an acetylene and argon gas environment. Morphological and compositional characterization of the resultant materials revealed that the composite consisted of a three-dimensional interconnected network of WO3 mesosponge layers conformally coated with a 5 nm thick carbon layer and grown directly on top of tungsten metal. The results demonstrated that the carbon-coated mesosponge WO3 layers exhibit a capacity retention of 87% after completion of 100 charge/discharge cycles, which is significantly higher than the values of 25% for the crystalline (without carbon coating) or 40% for the as-prepared mesosponge WO3 layers. The improved electrochemical response was attributed to the higher stability and enhanced electrical conductivity offered by the carbon coating layer.

Comparative electrochemical analysis of crystalline and amorphous anodized iron oxide nanotube layers as negative electrode for LIB.

This work is a comparative study of the electrochemical performance of crystalline and amorphous anodic iron oxide nanotube layers. These nanotube layers were grown directly on top of an iron current collector with a vertical orientation via a simple one-step synthesis. The crystalline structures were obtained by heat treating the as-prepared (amorphous) iron oxide nanotube layers in ambient air environment. A detailed morphological and compositional characterization of the resultant materials was performed via transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and Raman spectroscopy. The XRD patterns were further analyzed using Rietveld refinements to gain in-depth information on their quantitative phase and crystal structures after heat treatment. The results demonstrated that the crystalline iron oxide nanotube layers exhibit better electrochemical properties than the amorphous iron oxide nanotube layers when evaluated in terms of the areal capacity, rate capability, and cycling performance. Such an improved electrochemical response was attributed to the morphology and three-dimensional framework of the crystalline nanotube layers offering short, multidirectional transport lengths, which favor rapid Li(+) ions diffusivity and electron transport.

Electrically exploded silicon/carbon nanocomposite as anode material for lithium-ion batteries.

In this work, silicon (Si) containing carbon coated core-shell nanostructures were synthesized by electrical explosion of Si wires in ethanol solution followed by high energy mechanical milling (HEMM) process. Material characterization was carried-out using transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) analysis. HEMM led to very fine and amorphous Si particles in the presence of carbon and inactive Silicon-Carbide (SiC) matrix. These Si based nanocomposites, obtained through electrical explosion followed by HEMM (milled sample), exhibited enhanced electrochemical performance than unmilled nanocomposites, when evaluated as anode material for lithium-ion batteries (LIBs). On completion of (the) 1st cycle, milled and unmilled sample(s) showed specific discharge capacities around 825 mAh/g and 717 mAh/g, respectively. Interestingly, the coulombic efficiencies of milled and unmilled samples were 98.5% and 97% after 60th cycle respectively. The enhanced electrochemical performance is attributed to fine and amorphous Si based nanocomposite obtained through HEMM process.