Atoms in Lithiated Carbon Fibres

Abstract: Carbon fibres are key constituents of structural batteries, in which electrochemical energy storage and mechanical load bearing are merged in one multifunctional device. Here carbon fibres simultaneously act as structural reinforcement by carrying load and as battery electrode by hosting lithium (Li)-ions in its microstructure. However, conventional carbon fibres are not designed to be multifunctional. To enable carbon fibres with optimised multifunctional capabilities, a fundamental understanding of their microstructure, chemical information and interaction with Li is required. In this thesis, mass spectrometry and electron spectroscopy techniques are developed and used to elucidate the atomic distribution, configuration, and interaction in commercial carbon fibres used in structural batteries. Here the methodology of analysing Li in carbon fibres with atom probe tomography (APT) and Auger electron spectroscopy (AES) is demonstrated. Synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES) reveals that certain chemical states of N heteroatoms, pyridinic and pyrrolic, are connected to enhanced electrochemical performance of carbon fibres. AES shows that: Li distributes throughout the entire carbon fibre; the amount of trapped Li is higher and concentrated towards the centre of the fibre at increased discharge rates; Li is initially inserted in amorphous domains and with increased states of lithiation in crystalline domains; and Li plating can occur on individual fibres without spreading to adjacent fibres. APT on lithiated carbon fibres shows that: the distribution of Li is independent of the distribution of N heteroatoms; trapped Li is distributed uniformly in all domains; and Li agglomerates at elevated states of lithiation. The work presented in this thesis paves the way for analysis of carbon-based battery materials with APT and AES. Furthermore, the work unveils much of the interplay between carbon fibre and Li and deepens the understanding of the design parameters for tailoring multifunctional carbon fibres used in improved structural batteries.