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.

Piezoresponse force microscopy (PFM) has emerged as a powerful tool to characterize piezoelectric, ferroelectric, and multiferroic materials on the nanometer level. Much of the driving force for the broad adoption of PFM has been the intense research into piezoelectric properties of thin films, nanoparticles, and nanowires of materials as dissimilar as perovskites, nitrides, and polymers. Recent recognition of limitations of single-frequency PFM, notably topography-related cross-talk, has led to development of novel solutions such band-excitation (BE) methods. In parallel, the need for quantitative probing of polarization dynamics has led to emergence of complex time-and voltage spectroscopies, often based on acquisition and analysis of multidimensional datasets. In this perspective, we discuss the recent developments in multidimensional PFM, and offer several examples of spectroscopic techniques that provide new insight into polarization dynamics in ferroelectrics and multiferroics. We further discuss potential extension of PFM for probing ionic phenomena in energy generation and storage materials and devices.

Nonlinear dynamics underpin a vast array of physical phenomena ranging from interfacial motion to jamming transitions. In many cases, insight into the nonlinear behavior can be gleaned through exploration of higher order harmonics. Here, a method using band excitation scanning probe microscopy (SPM) to investigate higher order harmonics of the electromechanical response, with nanometer scale spatial resolution is presented. The technique is demonstrated by probing the first three harmonics of strain for a Pb(Zr1-xTix)O3 (PZT) ferroelectric capacitor. It is shown that the second order harmonic response is correlated with the first harmonic response, whereas the third harmonic is not. Additionally, measurements of the second harmonic reveal significant deviations from Rayleigh-type models in the form of a much more complicated field dependence than is observed in the spatially averaged data. These results illustrate the versatility of nth order harmonic SPM detection methods in exploring nonlinear phenomena in nanoscale materials.