The movement of lithium ions into and out of electrodes is central to the operation of lithium-ion batteries. Although this process has been extensively studied at the device level, it remains insufficiently characterized at the nanoscale level of grain clusters, single grains and defects. Here, we probe the spatial variation of lithium-ion diffusion times in the battery-cathode material LiCoO(2) at a resolution of ∼100 nm by using an atomic force microscope to both redistribute lithium ions and measure the resulting cathode deformation. The relationship between diffusion and single grains and grain boundaries is observed, revealing that the diffusion coefficient increases for certain grain orientations and single-grain boundaries. This knowledge provides feedback to improve understanding of the nanoscale mechanisms underpinning lithium-ion battery operation.
Mapping energy transformation pathways and dissipation on the nanoscale and understanding the role of local structure on dissipative behavior is a grand challenge for imaging in areas ranging from electronics and information technologies to efficient energy production. Here we develop a novel Scanning Probe Microscopy (SPM) technique in which the cantilever is excited and the response is recorded over a band of frequencies simultaneously rather than at a single frequency as in conventional SPMs. This band excitation (BE) SPM allows very rapid acquisition of the full frequency response at each point * Corresponding author, sergei2@ornl.gov 2 (i.e. transfer function) in an image and in particular enables the direct measurement of energy dissipation through the determination of the Q-factor of the cantilever-sample system. The BE method is demonstrated for force-distance and voltage spectroscopies and for magnetic dissipation imaging with sensitivity close to the thermomechanical limit. The applicability of BE for various SPMs is analyzed, and the method is expected to be universally applicable to all ambient and liquid SPMs.
Multiferroic materials showing coupled electric, magnetic and elastic orderings provide a platform to explore complexity and new paradigms for memory and logic devices. Until now, the deterministic control of non-ferroelectric order parameters in multiferroics has been elusive. Here, we demonstrate deterministic ferroelastic switching in rhombohedral BiFeO(3) by domain nucleation with a scanning probe. We are able to select among final states that have the same electrostatic energy, but differ dramatically in elastic or magnetic order, by applying voltage to the probe while it is in lateral motion. We also demonstrate the controlled creation of a ferrotoroidal order parameter. The ability to control local elastic, magnetic and torroidal order parameters with an electric field will make it possible to probe local strain and magnetic ordering, and engineer various magnetoelectric, domain-wall-based and strain-coupled devices.
We demonstrate a highly reproducible control of local electron transport through a ferroelectric oxide via its spontaneous polarization. Electrons are injected from the tip of an atomic force microscope into a thin film of lead-zirconate titanate, Pb(Zr0.2Ti0.8)O3, in the regime of electron tunneling assisted by a high electric field (Fowler-Nordheim tunneling). The tunneling current exhibits a pronounced hysteresis with abrupt switching events that coincide, within experimental resolution, with the local switching of ferroelectric polarization. The large spontaneous polarization of the PZT film results in up to 500-fold amplification of the tunneling current upon ferroelectric switching. The magnitude of the effect is subject to electrostatic control via ferroelectric switching, suggesting possible applications in ultrahigh-density data storage and spintronics.
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