Developing ultra-high strength in rare-earth-free Mg alloys using conventional extrusion process is a great challenge. What is even more difficult is to achieve such a goal at a lower processing cost. In this work, we report a novel low-alloyed Mg-2Sn-2Ca alloy (in wt. %) that exhibits tunable ultra-high tensile yield strength (360e440 MPa) depending on extrusion parameters. More importantly, there is little drop in mechanical properties of this alloy even when it is extruded at a speed several times higher than those used in the reported high strength Mg alloys. Examination of as-extruded microstructures of this Cacontaining Mg alloy reveals that the ultra-high strength is mainly associated with the presence of surprisingly submicron matrix grains (down to~0.32 mm). The results suggest that the Ca addition promotes accumulations of the pyramidal dislocations, which eventually transform into the low angular grain boundaries (LAGBs). The high number density of LAGBs separate the a-Mg matrix via either discontinuous dynamic recrystallization (DDRX) mechanism in the early stage or the continuous dynamic recrystallization (CDRX) mechanism in the later stage of extrusion, which effectively enhances the nucleation rates of the DRXed grains. More importantly, large amount of Ca segregation along LAGBs, accompanied with dynamically precipitated Mg 2 Ca nano-phases, are detected in the present nonseverely deformed samples. It is the combination of solute segregations and numerous Mg 2 Ca nanoprecipitates that contributes to the formation of the ultra-fine grains via pinning mechanism. The ultrafine grains size, Ca enrichment in most LAGBs, and residual Mg 2 Ca nano-precipitates would in turn contribute significantly to the enhancement of the yield strength of the as-extruded Mg-2Sn-2Ca (wt.%) alloy. The low content of alloying elements and the fast one-step extrusion process render the present alloys low-cost and thus have great potential in large-scale industry applications.
Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li 2 MnO 3 , we show through density functional theory calculations that a high energy orbital (lO 2p') at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO 4) 2− , and show that these groups stabilize the surface of Li 2 MnO 3 by depressing gas release and side reactions with the electrolyte. Experimental validation on Li 1.2 Ni 0.2 Mn 0.6 O 2 shows that sulfur deposition enhances stability of the cathode with 99.0% capacity remaining (194 mA h g −1) after 100 cycles at 1 C. Our work reveals a promising surface treatment to address the instability of highly charged layered cathode materials.
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