(Invited) Ultrahigh Areal Capacity Holey Graphene Air Cathodes for Li-O2 and Li-CO2 Batteries

Abstract

Advanced lithium (Li) batteries using gaseous cathode reactants such as oxygen (O2) and carbon dioxide (CO2) are attractive energy storage platforms because the gases are obtained externally and thus not accounted for in the total battery weight when fully charged. The discharge products at the cathode, typically Li2O2 for Li-O2 batteries and Li2CO3for Li-CO2 batteries, are insoluble in the electrolyte. Therefore, in order for such batteries to function properly, an “air cathode”, which is a conductive scaffold within the battery cell, is required as a physical location for cathode electrochemical reactions to occur. Prior research has identified many carbon nanomaterials such as carbon nanotubes and graphene as viable choices for air cathode scaffold, while various metallic and metal-free catalytic systems integrated onto carbon-based air cathodes have been developed to improve the sluggish discharge and charge reactions. For future practical applications, the air cathode must exhibit a usable capacity per unit electrode area, or areal capacity, a critical parameter that has been largely overlooked so far in this field. In order to achieve high areal capacity, the air cathode must exhibit a sufficient amount of accessible void volume per unit electrode area while maintaining the conductive scaffold integrity during the entire electrochemical process.Here we present an ultrathick, holey graphene-based air cathode platform fabricated from a facile dry compression process that exhibits remarkable areal capacity values. Holey graphene is a carbon nanomaterial derived from graphene, but with nanometer sized holes through the nanosheet thickness. The holes are generated in a controlled air oxidation process in which the defective carbon on the graphene surface are selectively oxidized and removed. The presence of these holes enhances mass transport through electrode thickness and also enables the unique dry-press fabrication process that is not achievable using other carbon scaffold materials. The dry-pressed holey graphene air cathode platform is compatible with catalyst incorporation to improve battery reaction kinetics. This platform also allows for novel engineering of electrode architectures not achievable using conventional electrode fabrication approaches. The applications of such highly versatile, ultrahigh areal capacity air cathode platforms to both Li-O2 and Li-CO2 battery chemistries will be discussed.