Tuning of Composition and Morphology of LiFePO4 Cathode for Applications in All Solid-State Lithium Metal Batteries

All solid-state rechargeable lithium metal batteries (SS-LMBs) are gaining more and more importance because of their higher safety and higher energy densities in comparison to their liquid-based counterparts. In spite of this potential, their low discharge capacities and poor rate performances limit them to be used as state-of-the-art SS-LMBs. This arise due to the low intrinsic ionic and electronic transport pathways within the solid components in the cathode during the fast charge/discharge processes. Therefore, it is necessary to have a cathode with good electron conducting channels to increase the active material utilization without blocking the movement of lithium ions. Since SS-LMBs require a different morphology and composition of the cathode, we selected LiFePO4 (LFP) as a prototype and, we have systematically studied the influence of the cathode composition by varying the contents of active material LFP, conductive additives (super C65 conductive carbon black and conductive graphite), ion conducting components (PEO and LiTFSI) in order to elucidate the best ion as well as electron conduction morphology in the cathode. In addition, a comparative study on different cathode slurry preparation methods was made, wherein ball milling was found to reduce the particle size and increase the homogeneity of LFP which further aids fast Li ion transport throughout the electrode. The SEM analysis of the resulting calendered electrode shows the formation of non-porous and crack-free structures with the presence of conductive graphite throughout the electrode. As a result, the optimum LFP cathode composition with solid polymer nanocomposite electrolyte (SPNE) delivered higher initial discharge capacities of 114 mAh g-1 at 0.2C rate at 30 ᴼC and 141 mAh g-1 at 1C rate at 70 ᴼC. When the current rate was increased to 2C, the electrode still delivered high discharge capacity of 82 mAh g-1 even after 500 cycle, which indicates that the optimum cathode formulation is one of the important parameters in building high rate and long cycle performing SS-LMBs.

Micro-Structural Design of Soft Solid Composite Electrolytes with Enhanced Ionic Conductivity

Electrolyte in a rechargeable Li-ion battery plays a critical role in determining its capacity and efficiency. While the typically used electrolytes in Li-ion batteries are liquid, soft solid electrolytes are being increasingly explored as an alternative due to their advantages in terms of increased stability, safety and potential applications in the context of flexible and stretchable electronics. However, ionic conductivity of solid polymer electrolytes is significantly lower compared to liquid electrolytes. In a recent work, we developed a theoretical framework to model the coupled deformation, electrostatics and diffusion in heterogeneous electrolytes and also established a simple homogenization approach for the design of microstructures to enhance ionic conductivity of composite solid electrolytes. Guided by the insights from the theoretical framework, in this paper, we ex- amine specific microstructures that can potentially yield significant improvement in the effective ionic conductivity. We numerically implement our theory in the open source general purpose finite element package FEniCS to solve the governing equations and present numerical solutions and insights on the effect of microstructure on the enhancement of ionic conductivity. Specifically, we investigate the effect of shape by considering ellipsoidal inclusions. We also propose an easily manufacturable microstructure that increases the ionic conductivity of the composite electrolyte by forty times, simply by the addition of dielectric columns parallel to the solid electrolyte phase.

Modeling of Twin Screw Extrusion of Polymeric Materials

An issue of modeling of twin-screw extrusion of polymeric materials is reviewed. The paper is written in honor of Prof. James L. White who was a pioneer in studying this issue. A global approach to process modeling is presented which includes solid polymer transport, polymer plasticating, and the flow of molten polymer. The methodology of CFD modeling of twin-screw extrusion is presented as well as the examples of this modeling which show the details of the process. Optimization and scaling of twin-screw extrusion are also covered. And finally, the future prospects of developments and research of twin screw extrusion is discussed.

Influence of Nano Filler (ZrO2) on Optical and Thermal Studies of Potassium Doped Polyethylene Oxide Solid Polymer Electrolytes

Solid polymer electrolyte films made with potassium doped Polyethylene oxide using ZrO2 as nanofiller (70PEO-30KBF4-x ZrO2 where x = 1, 2.5, 5, 7.5, & 10 wt% ­­) were prepared by solution casting technique. Optical and thermal properties of polymer electrolyte films were studied by using Optical absorption and DSC techniques. From Optical absorption spectra, it is observed that fundamental absorption edge is shifted towards the higher wavelength side (range 259- 297 nm) with increase of nano filler (ZrO­2) concentration (1-10 wt %). Optical band gap for all electronic transitions (p=1/2, 2, 2/3 and 1/3) are found to be increased as incorporation of nano filler (ZrO2) which confirms the structural rearrangements takes place in polymer electrolyte films. Optical band gap for indirect allowed transitions (p=1/2) are found to be in the range of 1.93-3.34eV. Decrease in Urbach energy (4.8eV- 1.4eV) is associated with decrease in defect formation in host polymeric matrix (PEO-KBF4) as a result of embedded nano filler (ZrO2). DSC spectra analysis of polymer electrolytes has showed melting temperatures in the range 63.63-73.71°C and highest crystallinity is found to be 85 % (10 wt % ZrO­2). Enthalpy values are elevated with increase in nanofiller composition (ZrO2) in the present polymer electrolyte films.Keywords: PEO based polymer electrolytes, Solid polymer electrolytes, Optical and Thermal studies.