On-chip lithium cells for electrical and structural characterization of single nanowire electrodes.

We present a transmission electron microscopy (TEM)-compatible, hybrid nanomachined, onchip construct for probing the structural and electrical changes in individual nanowire electrodes during lithium insertion. We have assembled arrays of individual beta-phase manganese dioxide (beta-MnO2) nanowires (NWs), which are employed as a model material system, into functional electrochemical cells through a combination of bottom-up (dielectrophoresis) and top-down (silicon nanomachining) unit processes. The on-chip NWs are electrochemically lithiated inside a helium-filled glovebox and their electrical conductivity is studied as a function of incremental lithium loading during initial lithiation. We observe a dramatic reduction in NW conductivity (on the order of two to three orders in magnitude), which is not reversed when the lithium is extracted from the nanoelectrode. This conductivity change is attributed to an increase in lattice disorder within the material, which is observed from TEM images of the lithiated NWs. Furthermore, electron energy loss spectroscopy (EELS) was employed to confirm the reduction in valence state of manganese, which occurs due to the transformation of MnO2 to LixMnO2.