Li‐rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO2 and LiMn2O4; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high‐energy lithium‐ion batteries. Herein, hexagonal La0.8Sr0.2MnO3−y (LSM) is used as a protective and phase‐compatible surface layer to stabilize the Li‐rich layered Li1.2Ni0.13Co0.13Mn0.54O2 (LM) cathode material. The LSM is MnOM bonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM‐coated LM delivers an enhanced reversible capacity of 202 mAh g−1 at 1 C (260 mA g−1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g−1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next‐generation of high‐energy Li‐ion batteries.
Li-rich layered oxides have attracted intense attention for lithium-ion batteries, as provide substantial capacity from transition metal cation redox simultaneous with reversible oxygen-anion redox. However, unregulated irreversible oxygen-anion redox leads to critical issues such as voltage fade and oxygen release. Here, we report a feasible NiFe2O4 (NFO) surface-coating strategy to turn the nonbonding coordination of surface oxygen into metal–oxygen decoordination. In particular, the surface simplex M–O (M = Ni, Co, Mn from MO6 octahedra) and N–O (N = Ni, Fe from NO6 octahedra) bonds are reconstructed in the form of M–O–N bonds. By applying both in operando and ex situ technologies, we found this heterostructural interface traps surface lattice oxygen, as well as restrains cation migration in Li-rich layered oxide during electrochemical cycling. Therefore, surface lattice oxygen behavior is significantly sustained. More interestingly, we directly observe the surface oxygen redox decouple with cation migration. In addition, the NFO-coating blocks HF produced from electrolyte decomposition, resulting in reducing the dissolution of Mn. With this strategy, higher cycle stability (91.8% at 1 C after 200 cycles) and higher rate capability (109.4 mA g–1 at 1 C) were achieved in this work, compared with pristine Li-rich layered oxide. Our work offers potential for designing electrode materials utilizing oxygen redox chemistry.
Azimuthal anisotropy retrieved from surface waves is important for constraining depthvarying deformation patterns in the crust and upper mantle. We present a direct inversion technique for the three-dimensional shear wave speed azimuthal anisotropy based on mixed-path surface wave traveltime data. This new method includes two steps: (1) inversion for the 3-D isotropic Vsv model directly from Rayleigh wave traveltimes and (2) joint inversion for both 3-D Vsv azimuthal anisotropy and additional 3-D isotropic Vsv perturbation. The joint inversion can significantly mitigate the trade-off between strong heterogeneity and anisotropy. With frequency-dependent ray tracing based on 2-D isotropic phase speed maps, the new method takes into account the ray-bending effect on surface wave propagation. We apply the new method to a regional array in Yunnan, southwestern China. Using Rayleigh wave phase velocity dispersion data in the period band of 5-40 s extracted from ambient noise interferometry, we obtain a 3-D model of shear wave speed and azimuthal anisotropy in the crust and uppermost mantle in Yunnan. This model reveals that two midcrust low-velocity zones are possible weak channels, and the azimuthal anisotropy at a depth of 5 to 30 km is mainly controlled by nearby strike-slip faults, some of which also approximately coincide with the lateral boundaries of the crustal low-velocity zones. Approximately south of 26°N, the upper crustal azimuthal anisotropy from our model is significantly different from the upper mantle anisotropy inferred by shear wave splitting, indicating different deformation styles between the crust and upper mantle in southern Yunnan.
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