Date of Award
Doctor of Philosophy in Chemistry
Brett L. Lucht
Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both the electrolyte solution and uncharged cathode particles were analyzed. The solid cathode particles were analyzed via scanning electron microscopy (SEM) whereas the electrolyte solution was analyzed using inductively coupled plasma mass spectroscopy (ICP-MS). The SEM analysis assists with elucidation of changes to the surfaces of the cathode particles. The ICP-MS of the electrolyte allows the determination of the extent of Mn and Ni dissolution. Samples of LiNi0.5Mn1.5O4 with different crystal surface facets were prepared to investigate the role of particle morphology in Mn and Ni dissolution. The factors affecting Mn and Ni dissolution and methods to inhibit dissolution will be discussed.
Knight, Brandon M., "PC BASED ELECTROLYTES WITH LIDFOB AS AN ALTERNATIVE SALT FOR LITHIUM-ION BATTERIES" (2014). Open Access Dissertations. Paper 242.