Revealing the Mechanism of Electrochemical Lithiation of Carbon Nanotube Fibers

Fabrics of continuous carbon nanotube fibers (CNTFs) are attractive materials for multifunctional energy storage devices, either as a current collector or as an active material. Despite a similar chemical composition, lithiation/delithiation in CNTFs is substantially different from that in traditional graphite electrodes. In CNTFs, this process is dominated by surface processes, insertion in the bundle interstices, electrochemical doping, and often-overlooked partial degradation of the sp 2 lattice upon cycling. Through extensive electrochemical analysis, together with in situ Raman spectroscopy measurements, we analyzed the complex lithiation behavior of highly crystalline CNTFs. CNTFs can store lithium reversibly with high specific capacity and rate capability, thanks to a large capacitive contribution. Upon lithiation, they undergo electrochemical doping, with longitudinal conductivity increasing by as much as 100%, concomitant with large downshifts in Raman spectra. However, CNTFs are also affected by high first-cycle irreversible capacity, voltage hysteresis, and amorphization upon cycling. Electrochemical analysis confirms that solid–electrolyte interphase formation is responsible for the first-cycle irreversible capacity. Voltage hysteresis is attributed primarily to the trapping of lithium ions in the interstices between stacked nanotubes. Another dominant feature is pre-existing defects, which promote capacitive storage but lead to progressive amorphization of the CNTFs. Indeed, it is evidenced that undesired amorphization is hindered in ultrapure CNTFs without preexisting defects.