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Title

INVESTIGATION OF STRUCTURE AND PROCESSING EFFECTS ON THE ELECTROCHEMICAL PERFORMANCE OF COBALT-FREE, LITHIUM- AND MANGANESE-RICH LAYERED OXIDE CATHODE FOR LIBS

Creator

Kucuk, Kamil

Date

2021

Description

Rechargeable Li-ion batteries (LIBs) have been widely used in a diverse range of energy storage systems because of their high energy and power...
Show moreRechargeable Li-ion batteries (LIBs) have been widely used in a diverse range of energy storage systems because of their high energy and power density, low self-discharge, and tolerable memory effect, compared to the conventional alkaline, lead acid, and nickel-cadmium (Ni/Cd) batteries. [2] Since not only cathodes materials control the energy density of a cell, but also the capacity of cathode material characteristically restricts the cell capacity (as well as about 40% of the cell cost results from the cost of cathode raw materials), the majority of studies on LIBs have been carried out on developing alternative cathodes with higher energy, lower cost, and more environmentally friendliness. [2], [3] From this perspective, both Co-free and lithium- & manganese-rich (LMRO) layered oxide MNF cathodes, Li1.2(MnxNiyFez)O2, have recently attracted great attention in lithium-ion battery (LIB) research for electric vehicles and energy storage devices due to their high capacities of over 250 mAhg−1 and being eco-friendly and inexpensive compared to the cobalt-based Li-rich Li1.2(NixMnyCoz)O2 and Ni-rich Li(NixMnyCoz)O2 (NMC), and LiCoO2 commercial cathodes. Replacing toxic and expensive Co in the LMRO cathodes with environmentally friendly and much cheaper Fe element has been extensively studied over the last two decades. It was suggested by Aryal, S. et. al., in 2018. [4] that the Li1.2(Mn0.50Ni0.20Fe0.10)O2 (MNF502010) Co-free LMRO MNF cathodes seem better in terms of capacity-retention with higher discharge capacity and less voltage fade compared to other MNF compositions. However, the MNF502010 cathode still suffers from its lower experimental capacity, compared to its expected theoretical capacity (270-455 mAhg−1), as well as capacity decay, voltage fade, poor rate capability, and thermal instability. In this dissertation, it is reported that comparable specific discharge capacity with less amount of voltage fading and capacity decay can be achieved by fluorine doping, synthesizing materials in large amounts (0.1 mol synthesis at least) with two-step firing, and then washing the obtained nanocomposites with H3PO4 to create Li3PO4 layer on the surface of bulk MNF composites. The specific discharge capacity and cycling performance of the Co-free MNF502010 cathodes were studied and enhanced by using and optimizing these approaches in this work for the first time. However, voltage fading and capacity decay are still remaining challenges, even if they are remarkably mitigated by applying these approaches. Structural changes due to layered to spinel transformation, less amount of monoclinic phase activation leading to structural deformation occurring after 1st charge, dissolution of the transition metals (TM), and oxygen release (loss of lattice oxygen) from the MNF material upon following electrochemical cycling at higher voltage (≥ 4.5V ) seem the main reasons behind these challenges, specifically the voltage fading and capacity decay.A series of fluorine-doped/undoped, Co-free MNF502010 nanocomposite cathode materials (Li1.2(Mn0.50Ni0.20Fe0.10)O2(1−x)F2x, briefly F-doped MNF) were synthesized by using a sol-gel technique. Firstly (Chapter 4), the fluorine was substituted for oxygen in the parent MNF compound in different fractions (0.00, 0.025, 0.05,0.075, 0.10, which means 0%, 2.5%, 5.0%, 7.5%, and 10%), in order to optimize the amount of fluorine for better performance; secondly (Chapter 5), a large batch (0.1mol, 10 times more than the previous batch) of 5%F-doped material was prepared by a modified sol-gel synthesis which is modified by heating at 700 ◦C for different time-periods; 7.5 hours (7.5h), 15 hours (15h, two-step firing, 7.5h + rest for 12h + 7.5h), instead of heating directly 15 hours (d15h), as done in the first chapter; finally (Chapter 6), H3PO4 treatment resulting in a non-uniform Li3PO4 layer on the bulk surface. These approaches were respectively applied on doped/undoped MNF502010 nano-composites, in order to overcome the challenges already mentioned above. Finally, the effects of these approaches on the structural, morphological, and electrochemical properties of MNF cathode materials were investigated by means of powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) with energy dispersive X-ray (EDS) analysis, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), galvanostatic charge-discharge cycling, and X-ray absorption spectroscopy (XAS, an element specific probe technique). Specifically, ex-situ XAS was performed at the Mn, Ni, and Fe K-edge and used to detect the changes both in the oxidation state of the transition metal (TM) ions and their local environments in order to get a better understanding of the improved performance of the composite materials, as well as their failure mechanism. Moreover, the EXAFS data were modeled to gain insight into the influence of these approaches on the electrochemical performance of both pristine (uncycled) and cycled electrodes (after the 100th discharge). From correlating the electrochemical performance of the modified/unmodified MNF nano-composite cathodes to their XANES and EXAFS analysis, the ability to achieve higher specific capacity is strongly dependent on the formation of a well-ordered layered structure and the amount of monoclinic component (Li2MnO3) activation resulting in higher redox-activity of the Mn cations. The long-term cyclability or capacity retention can be enhanced by heating the resulting powders with a two-step firing (instead of directly 15 hours) and washing them with 1wt%H3PO4 solution to create a Li3PO4 conductive and protective layer.
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