An increase in the amount of nickel in LiMO2 (M = Ni, Co, Mn) layered system is actively pursued in lithium‐ion batteries to achieve higher capacity. Nevertheless, fundamental effects of Ni element in the three‐component layered system are not systematically studied. Therefore, to unravel the role of Ni as a major contributor to the structural and electrochemical properties of Ni‐rich materials, Co‐fixed LiNi0.5+xCo0.2Mn0.3–xO2 (x = 0, 0.1, and 0.2) layered materials are investigated. The results, on the basis of synchrotron‐based characterization techniques, present a decreasing trend of Ni2+ content in Li layer with increasing total Ni contents. Moreover, it is discovered that the chex.‐lattice parameter of layered system is not in close connection with the interslab thickness related to actual Li ion pathway. The interslab thickness increases with increasing Ni concentration even though the chex.‐lattice parameter decreases. Furthermore, the lithium ion pathway is preserved in spite of the fact that the c‐axis is collapsed at highly deintercalated states. Also, a higher Ni content material shows better structural properties such as larger interslab thickness, lower cation disorder, and smoother phase transition, resulting in better electrochemical properties including higher Li diffusivity and lower overpotential when comparing materials with lower Ni content.

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A three dimensional vanadium pentoxide/reduced graphene oxide/carbon nanotube (3D V2O5/RGO/CNT) composite is synthesized by microwave-assisted hydrothermal method. The combination of 2D RGO and 1D CNT establishes continuous 3D conductive network, and most notably, the 1D CNT is designed to form hierarchically porous structure by penetrating into V2O5 microsphere assembly constituted of numerous V2O5 nanoparticles. The highly porous V2O5 microsphere enhances electrolyte contact and shortens Li+ diffusion path as a consequence of its developed surface area and mesoporosity. The successive phase transformations of 3D V2O5/RGO/CNT from α-phase to ε-, δ-, γ-, and ω-phase and its structural reversibility upon Li+ intercalation/de-intercalation are investigated by in situ XRD analysis, and the electronic and local structure reversibility around vanadium atom in 3D V2O5/RGO/CNT is observed by in situ XANES analysis. The 3D V2O5/RGO/CNT achieves a high capacity of 220 mAh g−1 at 1 C after 80 cycles and an excellent rate capability of 100 mAh g−1 even at a considerably high rate of 20 C. The porous 3D V2O5/RGO/CNT structure not only provides facile Li+ diffusion into bulk but contributes to surface Li+ storage as well, which enables the design of 3D V2O5/RGO/CNT composite to become a promising cathode architecture for high performance LIBs.

The conventional view of conversion reaction is based on the reversibility, returning to an initial material structure through reverse reaction at each cycle in cycle life, which impedes the complete understanding on a working mechanism upon a progression of cycles in conversion-reaction-based battery electrodes. Herein, a series of tin-doped ferrites (Fe3–x Sn x O4, x = 0–0.36) are prepared and applied to a lithium-ion battery anode. By achieving the ideal reoxidation into SnO2, the Fe2.76Sn0.24O4 composite anchored on reduced graphene oxide shows a high reversible capacity of 1428 mAh g–1 at 200 mA g–1 after 100 cycles, which is the best performance of Sn-based anode materials so far. Significantly, a newly formed γ-FeOOH phase after 100 cycles is identified from topological features through synchrotron X-ray absorption spectroscopy with electronic and atomic structural information, suggesting the phase transformation from magnetite to lepidocrocite upon cycling. Contrary to the conventional view, our work suggests a variable working mechanism in an iron-based composite with the dynamic phases from iron oxide to iron oxyhydroxide in the battery cycle life, based on the reactivity of metal nanoparticles formed during reaction toward the solid electrolyte interface layer.