The highest theoretical capacity (3860 mAh/g) and lowest redox potential (-3.04 V vs standard hydrogen electrode) makes lithium metal as a promising anode for next generation high energy density batteries.¹ Despite theoretical advantages, there are challenges in commercializing Li metal anodes such as low coulombic efficiency, dendrite formation and poor cycling life. Dendrite formation can cause short circuit and thermal runaway, which is a safety concern. Among the various ways to mitigate the Li dendrite formation, using three-dimensional (3D) current collectors with lithiophilic properties and low tortuous pore architecture is an effective way. It would decrease the local current density owing to high active surface area while accommodating the large volume change during prolonged charge/discharge cycles.

Vertically aligned carbon nanofibers (VACNF) have been demonstrated as a promising candidate as a lithiophilic 3D host for lithium metal anodes as they possess unique conically stacked lithiophilic graphitic edges with O containing functional groups and high N doping (~6.5 at%).² However, a fundamental, deeper understanding of the Li plating/stripping processes on such 3D electrodes has not been developed yet. Here in, we investigate the lithium nucleation and growth processes and its morphological changes using ex-situ structural characterization techniques such as SEM and cryo-TEM. The composition of the solid electrolyte interface is investigated using XPS. In-situ Raman spectroscopic studies provided further information about the changes that occur in the VACNFs during Li plating/stripping processes and Li intercalation/deintercalation processes. Ion-beam sputtering of an ultrathin gold layer onto the VACNFs was found to further improve the lithiophilicity of the 3D electrode and lead to more reversible Li metal plating/stripping. The new insights on the electrodeposition of lithium in 3D electrodes and its relationship with the enhanced cycle life acquired using various analytical tools will be discussed.

Reference:

(1) Manthiram, A.; Chung, S.-H.; Zu, C. Lithium–Sulfur Batteries: Progress and Prospects. Advanced Materials 2015, 27 (12), 1980–2006.

(2) Chen, Y.; Elangovan, A.; Zeng, D.; Zhang, Y.; Ke, H.; Li, J.; Sun, Y.; Cheng, H. Vertically Aligned Carbon Nanofibers on Cu Foil as a 3D Current Collector for Reversible Li Plating/Stripping toward High-Performance Li–S Batteries. Advanced Functional Materials 2020, 30 (4), 1906444.