From atomic force microscopy (AFM) experiments, we report a new phenomenon in which the dissolution rate of fused silica is enhanced by more than 5 orders of magnitude by simply pressing a second, dissimilar surface against it and oscillating the contact pressure at low kHz frequencies in deionized water. The silica dissolution rate enhancement was found to exhibit a strong dependence on the pressure oscillation frequency consistent with a resonance effect. This harmonic enhancement of the silica dissolution rate was only observed at asymmetric material interfaces (e.g., diamond on silica) with no evidence of dissolution rate enhancement observed at symmetric material interfaces (i.e., silica on silica) within the experimental time scales. The apparent requirement for interface dissimilarity, the results of analogous experiments performed in anhydrous dodecane, and the observation that the silica “dissolution pits” continue to grow in size under contact stresses well below the silica yield stress refute a mechanical deformation or chemo-mechanical origin to the observed phenomenon. Instead, the silica dissolution rate enhancement exhibits characteristics consistent with a previously described ‘electrochemical pressure solution’ mechanism, albeit, with greatly amplified kinetics. Using a framework of electrochemical pressure solution, an electrochemical model of mineral dissolution, and a recently proposed “surface resonance” theory, we present an electro-chemo-mechanical mechanism that explains how oscillating the contact pressure between dissimilar surfaces in water can amplify surface dissolution rates by many orders of magnitude. This reaction rate enhancement mechanism has implications not only for dissolution but also for potentially other reactions occurring at the solid–liquid interface, e.g. catalysis.

Employing high-voltage Ni-rich cathodes in Li metal batteries (LMBs) requires stabilization of the electrode/electrolyte interfaces at both electrodes. A stable solid–electrolyte interphase (SEI) and suppression of active material pulverization remain the greatest challenges to achieving efficient long-term cycling. Herein, studies of NMC622 (1 mAh cm–2) cathodes were performed using highly concentrated N-methyl-N-propylpyrrolidinium bis­(fluorosulfonyl)­imide (C3mpyrFSI) 50 mol % lithium bis­(fluorosulfonyl)­imide (LiFSI) ionic liquid electrolyte (ILE). The resulting SEI formed at the cathode enabled promising cycling performance (98.13% capacity retention after 100 cycles), and a low degree of ion mixing and lattice expansion was observed, even at an elevated temperature of 50 °C. Fitting of acquired impedance spectra indicated that the SEI resistivity (R SEI) had a low and stable contribution to the internal resistivity of the system, whereas active material pulverization and secondary grain isolation significantly increased the charge transfer resistance (R CT) throughout cycling.

A new method of direct‐write nanolithography that is able to rapidly etch silica surfaces under a scanning atomic force microscopy (AFM) probe in tapping mode (TM) is reported. In this lithography technique, silica surfaces are etched using a recently described electro‐chemo‐mechanical phenomenon of frequency enhanced electrochemical pressure solution (FEEPS). In FEEPS, the tapping of the AFM tip generates oscillations of the Stern potential at the silica‐water interface that can accelerate the silica dissolution kinetics by more than 5–6 orders of magnitude when surface resonance states are achieved; i.e., when the oscillation frequency is in phase with the dynamics of interfacial chemical reaction steps. By scanning silica surfaces in TM, silica is selectively dissolved below the tapping tip as it is scanned. The FEEPS accelerated silica dissolution rates can generate etched features with depths of more than 60 nm in a single AFM tip pass. The rate of etching can be controlled easily by varying the scanning rate or by modulating the tapping frequency. This fine control over the silica etching process and because material is removed (dissolved) rather than displaced as with nanoscratching, the FEEPS process lends itself to gray‐scale nanolithography which is demonstrated.

No abstract