This report focuses on the relatively new salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), and its functionality together with a silicon based composite electrode in a half-cell lithium ion battery context. LiTDI is a promising alternative to the commonly used LiPF6 salt because it does not form HF which can decompose the oxide layer on Si. The formation of a solid electrolyte interphase (SEI) as well as the development of the active Si-particles are investigated during the first electrochemical lithiation and de-lithiation. Characterizations are carried out at different state of charge with scanning electron microscopy (SEM) as well as hard x-ray photoelectron spectroscopy (HAXPES) at two different photon energies. This enables a depth resolved picture of the reaction processes and gives an idea of the chemical buildup of the SEI. The SEI is formed by solvent and LiTDI decomposition products and its composition is similar to SEI formed by other carbonate based electrolytes. The LiTDI salt or its decomposition products are not in itself reactive towards the active Si-material and no unwanted side reactions occurs with the active Si-particles. Despite some decomposition of the LiTDI salt, it is a promising alternative for electrolytes aimed towards Si-based electrodes.
Lithium-ion batteries have been widely used as power supplies for portable electronic devices due to their higher gravimetric and volumetric energy densities compared to other electrochemical energy storage technologies, such as lead-acid, Ni-Cd and Ni-MH batteries. Developing a novel battery chemistry, ‘‘all silicon lithium-ion batteries’’, using lithium iron silicate as the cathode and silicon as the anode, is the primary aim of this Ph.D project. This licentiate thesis is focused on improving the performance of the silicon anode via optimization of electrolyte composition and electrode formulation. Fluoroethylene carbonate (FEC) was investigated as an electrolyte additive for silicon composite electrodes, and both the capacity retention as well as coulombic efficiency were significantly improved by introducing 10 wt% FEC into the LP40 electrolyte. This is due to the formation of a stable SEI, which mainly consisted of FEC decomposition products of LiF, -CHFOCO2-, etc. The chemical composition of the SEI was identified by synchrotron radiation based photoelectron spectroscopy. This conformal SEI prevented formation of large amounts of cracks and continues electrolyte decomposition on the silicon electrode. An alternative lithium salt, lithium 4,5-dicyano-2-trifluoromethanoimidazole (LiTDI), was studied with the silicon electrode in this thesis. The SEI formation led to a rather low 1st cycle coulombic efficiency of 44.4%, and the SEI layer was found to contain hydrocarbon, ether-type and carbonate-type species. Different to conventional composite silicon electrodes, which require heavy and expensive copper current collector, a flexible silicon electrode, consisted of only silicon nanopowder, Cladophora nanocellulose and carbon nanotube, was facilely prepared via vacuum filtration. The electrode showed good mechanical, long-term cycling as well as rate capability performance.
This thesis is focusing on the challenges when using Si as a possible new negative electrode material in Li-ion batteries. The overall aim is to contribute to a general understanding of the processes in the Si electrode, to identify aging mechanisms, and to evaluate how they influence the cycling performance. Another objective is to investigate how photoelectron spectroscopy (PES) can be used to analyze these mechanisms.
LiPF6 based electrolytes are aggressive towards the oxide layer present at the surface of the Si particles. With the use of fluoroethylene carbonate (FEC) as an electrolyte additive the cycling performance is improved, but the oxide layer is still affected. A recently developed salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), is shown not to have any detrimental effects on the oxide. The SEI with FEC and vinylene carbonate (VC) as contains a high concentration of LiF and polymeric carbonate species and this composition seems to be beneficial for the cycling performance, but the results indicate that additional aging mechanisms occur. Therefore, electrochemical analysis is performed and confirms a continuous SEI formation. However, it also reveals a self-discharge mechanism and that a considerable amount of Li is remaining in the Si material after standard cycling.
PES is used in this work to analyze the SEI-layers as well as the surface and the bulk of the Si material. With this technique it is hence possible to distinguish changes in the Si material as a function of lithiation. To improve the data interpretation of PES spectra, a range of battery electrode model systems are investigated. These results show shifts of the SEI peaks relative to the electrode specific peaks as a result of the SEI thickness and the presence of a dipole layer. Also other electronically insulating composite electrode components show relative peak shifts as a function of the electrochemical potential.
To summarize, these studies investigate a number of well recognized aging mechanisms in detail and also establish additional processes contributing to aging in Si electrodes. Furthermore, this work highlights phenomena that influence data interpretation of PES measurements from battery materials.