Thin Films As a Platform for Understanding the Conversion Mechanism of FeF2 Cathodes in Lithium-Ion Microbatteries

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Conversion material electrodes such as FeF2 possess the potential to deliver transformative improvements in lithium ion battery performance because they permit a reversible change of more than one Li-ion per 3d metal cation. They outperform current state of the art intercalation cathodes such as LiCoO2, which have volumetric and gravimetric energy densities that are intrinsically limited by single electron transfer. Current studies focus on composite electrodes that are formed by mixing with carbon (FeF2-C), wherein the carbon is expected to act as a binder to support the matrix and facilitate electronic conduction. These binders complicate the understanding of the electrode-electrolyte ... continued below

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xix, 159 pages : illustrations (chiefly color)

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Santos-Ortiz, Reinaldo August 2015.

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  • Santos-Ortiz, Reinaldo

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Conversion material electrodes such as FeF2 possess the potential to deliver transformative improvements in lithium ion battery performance because they permit a reversible change of more than one Li-ion per 3d metal cation. They outperform current state of the art intercalation cathodes such as LiCoO2, which have volumetric and gravimetric energy densities that are intrinsically limited by single electron transfer. Current studies focus on composite electrodes that are formed by mixing with carbon (FeF2-C), wherein the carbon is expected to act as a binder to support the matrix and facilitate electronic conduction. These binders complicate the understanding of the electrode-electrolyte interface (SEI) passivation layer growth, of Li agglomeration, of ion and electron transport, and of the basic phase transformation processes under electrochemical cycling. This research uses thin-films as a model platform for obtaining basic understanding to the structural and chemical foundations of the phase conversion processes. Thin film cathodes are free of the binders used in nanocomposite structures and may potentially provide direct basic insight to the evolution of the SEI passivation layer, electron and ion transport, and the electrochemical behavior of true complex phases. The present work consisted of three main tasks (1) Development of optimized processes to deposit FeF2 and LiPON thin-films with the required phase purity and microstructure; (2) Understanding their electron and ion transport properties and; (3) Obtaining insight to the correlation between structure and capacity in thin-film microbatteries with FeF2 thin-film cathode and LiPON thin-film solid electrolyte. Optimized pulsed laser deposition (PLD) growth produced polycrystalline FeF2 films with excellent phase purity and P42/mnm crystallographic symmetry. A schematic band diagram was deduced using a combination of UPS, XPS and UV-Vis spectroscopies. Room temperature Hall measurements reveal that as-deposited FeF2 is n-type with an electron mobility of 0.33 cm2/V.s and a resistivity was 0.255 Ω.cm. The LiPON films were deposited by reactive sputtering in nitrogen, and the results indicate that the ionic conductivity is dependent on the amount of nitrogen incorporated into the film during processing. The highest ionic conductivity obtained was 1.431.9E-6 Scm-1 and corresponded to a chemical composition of Li1.9PO3.3N.21. FeF2/LiPON thin films microbatteries were assembled using a 2032 coin cell configuration and subjected to Galvanostatic cycling. HRTEM and EELS spectroscopy where performed across the FeF2/LiPON interface of samples cycled once 15 times in their lithiated and delithiated states to understand the relationship between microstructural evolution and capacity. The EELS measurements provided evidence of a three-phase conversion reaction over the first discharge described by FeF2 +2e-+2Li+↔Fe +LiF, and of incomplete reconversion back to FeF2 after the 1st cycle resulting in new Fe0 and LiF phases in delithiated samples. This incomplete conversion results in (a) a smaller phase fraction of FeF2 participating in the conversion process subsequently and (b) the formation of LiF which is resistive to both electron and ion transport. This results in the observed drastic drop in capacity after the1st cycle. More study to understand the reconversion reaction pathways is required to fully exploit the potential of FeF2 and other conversion materials as cathodes in Li ion batteries.

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xix, 159 pages : illustrations (chiefly color)

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  • August 2015

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  • March 4, 2016, 4:14 p.m.

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  • May 16, 2017, 7:41 a.m.

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Santos-Ortiz, Reinaldo. Thin Films As a Platform for Understanding the Conversion Mechanism of FeF2 Cathodes in Lithium-Ion Microbatteries, dissertation, August 2015; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc804977/: accessed November 23, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .