Date of Award

Spring 1-1-2016

Document Type


Degree Name

Doctor of Philosophy (PhD)


Chemical & Biochemical Engineering

First Advisor

Charles B. Musgrave

Second Advisor

Doug Gin

Third Advisor

Will Medlin

Fourth Advisor

SeHee Lee

Fifth Advisor

Al Weimer


Lithium ion battery technologies suffer from limitations in performance, such as capacity fading, due in part to degradation of the cathode and electrolyte materials. Quantum chemical simulations were employed to investigate the reactions leading to degradation of LiCoO2 cathodes and the electrolyte molecules. Formation of HF in the electrolyte resulting from reaction between PF5 and H2O impurities was first investigated. This research predicts HF is produced as a result of PF5 complexing with H2O, then reacting through ligand exchange to form HF and PF4OH with an activation barrier of 1.18 eV and reaction enthalpy of 0.15 eV. HF undergoes dissociative adsorption at that the (101 4) surface of LiCoO2 without a barrier, leading to formation of LiF-Li+ precipitates and H2O on the surface with a reaction energy of -2.41 eV. The formation of H2O is of particular concern because H2O drives further formation of HF in the electrolyte, resulting in an autocatalytic cycle of degradation. These findings indicate that HF initially occurs in low concentrations rapidly increases due to H2O generation upon HF attack. Reduction in capacity fading is observed in alumina ALD coated LiCoO2 cathodes and we have investigated a monolayer alumina coating on the LiCoO2 (101 4) surface to identify the mechanism by which the alumina coating protects the cathode surface. We have found that HF will preferentially dissociate at the alumina coating with a reaction energy of -2.84 eV and without any resolvable barrier to dissociation. Additionally, our calculations predict that H2O does not form as a result of HF dissociation at the alumina monolayer; instead HF dissociation produces neighboring hydroxyl sites on the alumina surface. Consequently, the alumina coating prevents the autocatalytic degradation of the cathode by sequestering HF impurities in the alumina film. Finally, we found that Lewis acid-base complexation between ethylene carbonate (EC) electrolyte molecules and PF5 or the LiCoO2 surface weaken C-O bonds in the EC ring, lowering the barrier to dissociate these bonds and causing EC degradation to be more exothermic. We present detailed mechanisms describing Lewis acid activated EC ring opening reactions to form either CO2 or EC oligomers.