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Ultrahigh surface-to-volume ratio in nanoscale materials, could dramatically facilitate mass transport, leading to surface-mediated diffusion similar to Coble-type creep in polycrystalline materials. Unfortunately, the Coble creep is just a conceptual model, and the associated physical mechanisms of mass transport have never been revealed at atomic scale. Akin to the ambiguities in Coble creep, atomic surface diffusion in nanoscale crystals remains largely unclear, especially when mediating yielding and plastic flow. Here, by using in situ nanomechanical testing under high-resolution transmission electron microscope, we find that the diffusion-assisted dislocation nucleation induces the transition from a normal to an inverse Hall-Petch-like relation of the strength-size dependence and the surface-creep leads to the abnormal softening in flow stress with the reduction in size of nanoscale silver, contrary to the classical “alternating dislocation starvation” behavior in nanoscale platinum. This work provides insights into the atomic-scale mechanisms of diffusion-mediated deformation in nanoscale materials, and impact on the design for ultrasmall-sized nanomechanical devices.

Mn‐redox‐based oxides and oxyfluorides are considered the most promising earth‐abundant high‐energy cathode materials for next‐generation lithium‐ion batteries. While high capacities are obtained in high‐Mn content cathodes such as Li‐ and Mn‐rich layered and spinel‐type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn‐rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation‐disordered rocksalt (DRX) cathode (Li_1.1Mn_0.8Ti_0.1O_1.9F_0.1, an ultrahigh capacity of ≈320 mAh g⁻¹(energy density of ≈900 Wh kg⁻¹) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn⁴⁺and Li⁺vacancies promotes local cation ordering, leading to the formation of domains of a “δphase” within the disordered framework. On deep discharge, Mn⁴⁺reduction, along with Li⁺insertion transform the structure to a partially ordered DRX phase with aβ′‐LiFeO₂‐type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high‐Mn DRXbut also provide guidance for the future development of Mn‐based, high‐energy density oxide, and oxyfluoride cathode materials.

The practical application of lithium (Li) metal anode (LMA) is still hindered by non‐uniformity of solid electrolyte interphase (SEI), formation of “dead” Li, and continuous consumption of electrolyte although LMA has an ultrahigh theoretical specific capacity and a very low electrochemical redox potential. Herein, a facile protection strategy is reported for LMA using a double layer (DL) coating that consists of a polyethylene oxide (PEO)‐based bottom layer that is highly stable with LMA and promotes uniform ion flux, and a cross‐linked polymer‐based top layer that prevents solvation of PEO layer in electrolytes. Li deposited on DL‐coated Li (DL@Li) exhibits a smoother surface and much larger size than that deposited on bare Li. The LiF/Li₂O enriched SEI layer generated by the salt decomposition on top of DL@Li further suppresses the side reactions between Li and electrolyte. Driven by the abovementioned advantageous features, the DL@Li||LiNi_0.6Mn_0.2Co_0.2O₂cells demonstrate capacity retention of 92.4% after 220 cycles at a current density of 2.1 mA cm^–2(C/2 rate) and stability at a high charging current density of 6.9 mA cm^–2(1.5 C rate). These results indicate that the DL protection is promising to overcome the rate limitation of LMAs and high energy‐density Li metal batteries.