Invited: In Situ Characterization of Plasma Assisted Hydrogenation/Fluorination of Graphene and CFx Battery Applications

Monolayer graphene synthesized by chemical vapor deposition was subjected to controlled and sequential hydrogenation using RF plasma while monitoring its electrical properties in-situ. Low temperature transport properties, viz., electrical resistance (R), thermopower (S), Hall mobility (m), and magneto-resistance (MR) were measured for each sample and correlated with ex-situ Raman scattering and X-ray photoemission (XPS) characteristics. For weak-hydrogenation, the transport is seen to be governed by electron diffusion and low temperature transport properties show metallic behavior (conductance G remains non-zero as 0). For strong-hydrogenation, the transport is found to be describable by variable range hopping (VRH) and the low T conductance shows insulating behavior (0 as 0). Weak localization (WL) behavior is seen with a negative MR for weakly-hydrogenated graphene and this WL effects are seen to diminish as the hydrogenation progresses. A clear transition to strong localization (SL) is evident with the emergence of pronounced negative MR for strongly-hydrogenated graphene. 

            Multi-walled carbon nanotubes synthesized using fluidized bed chemical vapor deposition technique were fluorinated sequentially to prepare a series of CFx battery electrodes. Primary battery performance was tested using CFx as a cathode against Li. Fully fluorinated MWNTs showed capacity exceeding 815 mAh/g while partially fluorinated samples showed systematically lowered capacity with decreasing x (in CFx). However, fully fluorinated MWCNTs showed distinctly low rechargeable capacity compared to the subfluorinated samples when used as an anode against Li. Mildly fluorinated MWNTs show high capacity and better stability during charge/discharge cycles. High concentrations of fluorine seem to affect capacity retention due to the increased defect densities and reduced electronic conduction. These defects of nanotubes will provide additional pathways for lithium ions to diffuse within the core of the fluorinated structure and to access the electrochemically active C-F sites. XRD, XPS, and Raman spectroscopy were utilized to characterize the samples. Finally the electrochemical performance of fluorinated MWNTs was compared with that of Natural Chinese Graphite (NCG).