Lithium titanate as anode material in lithium-ion batteries -A surface study

University dissertation from Uppsala : Uppsala universitet

Abstract: The ever increasing awareness of the environment and sustainability drives research to find new solutions in every part of society. In the transport sector, this has led to a goal of replacing the internal combustion engine (ICE) with an electrical engine that can be powered by renewable electricity. As a battery for vehicles, the Li-ion chemistries have become dominant due to their superior volumetric and gravimetric energy densities. While promising, electric vehicles require further improvements in terms of capacity and power output before they can truly replace their ICE counterparts. Another aspect is the CO2 emissions over lifetime, since the electric vehicle itself presently outlives its battery, making battery replacement necessary. If the lifetime of the battery could be increased, the life-cycle emissions would be significantly lowered, making the electric vehicle an even more suitable candidate for a sustainable society. In this context, lithium titanium oxide (LTO) has been suggested as a new anode material in heavy electric vehicles applications due to intrinsic properties regarding safety, lifetime and availability. The LTO battery chemistry is, however, not fully understood and fundamental research is necessary for future improvements. The scope of this project is to investigate degradation mechanisms in LTO-based batteries to be able to mitigate these and prolong the device lifetime so that, in the end, a suitable chemistry for large scale applications can be suggested. The work presented in this licentiate thesis is focused on the LTO electrode/electrolyte interface. Photoelectron spectroscopy (PES) was applied to determine whether the usage of LTO would prevent anode-side electrolyte decomposition, as suggested from the intercalation potential being inside the electrochemical stability window of common electrolytes. It has been found that electrolyte decomposition indeed occurs, with mostly hydrocarbons of ethers, carboxylates, and some inorganic lithium fluoride as decomposition products, and that this decomposition to some extent ensued irrespective of electrochemical battery operation activity. Second, an investigation into how crossover of manganese ions from Mn-based cathodes influences this interfacial layer has been conducted. It was found, using a combination of high-energy x-ray photoelectron spectroscopy (HAXPES) and near-edge x-ray absorption fine structure (NEXAFS) that although manganese is present on the LTO anode surface when paired with a common manganese oxide spinel cathode, the manganese does little to alter the surface chemistry of the LTO electrode.