Neutron depth profiling benchmarking and analysis of applications to lithium ion cell electrode and interfacial studies research
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The role of the lithium ion cell is increasing with great intensity due to global concerns for the decreased use of fossil fuels as well as the growing popularity of portable electronics. With the dramatic increase in demand for these cells follows an outbreak of research to optimize the lithium ion cells in terms of safety, cost, and also performance. The work shown in this dissertation sets out to distinguish the role of Neutron Depth Profiling (NDP) in the expanding research of lithium ion cells. Lithium ions play the primary role in the performance of lithium ion batteries. Moving from anode to cathode, and cathode to anode, the lithium ions are constantly being disturbed during the cell’s operation. The ability to accurately determine the lithium’s behavior within the electrodes of the cell after different operating conditions is a powerful tool to better understand the faults and advantages of particular electrode compositions and cell designs. NDP has this ability through the profiling of 6 Li. This research first validates the ability of The University of Texas NDP (UTNDP) facility to accurately profile operated lithium ion cell electrodes to a precision within 2% over 10 µm for concentration values, and with a precision for depth measurements within 77 nm. The validation of the UT-NDP system is performed by comparing UT-NDP profiles to those from the NIST-NDP system, from the Secondary Ion Mass Spectrometry (SIMS) technique, and also from Monte Carlo n-Particle (MCNPX) code simulations. All of the comparisons confirmed that the UT-NDP facility is fully capable of providing accurate depth profiles of lithium ion cell electrodes in terms of depth, shape of distribution, and concentration. Following the validation studies, this research investigates three different areas of lithium ion cell research and provides analysis based on NDP results. The three areas of investigation include storage of cells at temperature, cycling of cells, and the charging of cells at different current rates. The results conclude that NDP is a valuable asset to the characterization of the Solid Electrolyte Interface (SEI) growth as a function of storage time. The NDP results were able to conclude that LiFePO4 cell anodes have a factor of 21 times slower rate of SEI growth than anodes from LiFePSO4. This indicates that the capacity fade of the LiFePO4 cell will be less than that of the LiFePSO4 cell due to storage at 50ºC. Furthermore, NDP was able to conclude that cycling of cells had little effect on the lithium concentration within the cathode materials. The lithium concentration was found to be uniform throughout the first 10 µm of the LiFePO4 and LiNi1/3Mn1/3Co1/3O2 cathodes. These measurements agreed with the initial hypothesis. However, NDP analysis of cells charged at different current rates found that lithium was concentrating within the first 2 µm of the cathode’s surface at the electrode-electrolyte interface. This was an unexpected conclusion, but the results also concluded that effect of the lithium concentrating near the surface is amplified by charging the cells at higher current rates. The ultimate conclusion of this research was that NDP is capable of providing invaluable insight to the behavior of lithium within the electrodes of lithium ion cells. It is the author’s conclusion that NDP may be most useful in the investigation of SEI layers and their variation according to electrode composition, electrolyte compositions, and the conditions, such as temperature, to which the cells are exposed.