Poor electrical conductivity and mechanical instability are two major obstacles to realizing high performance of MnO2 as pseudocapacitor material. The construction of unique hierarchical core-shell nanostructures, therefore, plays an important role in the efficient enhancement of the rate capacity and the stability of this material. We herein report the fabrication of a hierarchical α-MnO2 nanowires@ultrathin δ-MnO2 nanosheets core-shell nanostructure by adopting a facile and practical solution-phase technique. The novel hierarchical nanostructures are composed of ultrathin δ-MnO2 nanosheets with a few atomic layers growing well on the surface of the ultralong α-MnO2 nanowires. The first specific capacitance of hierarchical core-shell nanostructure reached 153.8 F g(-1) at the discharge current density of as high as 20 A g(-1), and the cycling stability is retained at 98.1% after 10,000 charge-discharge cycles, higher than those in the literature. The excellent rate capacity and stability of the hierarchical core-shell nanostructures can be attributed to the structural features of the two MnO2 crystals, in which a 1D α-MnO2 nanowire core provides a stable structural backbone and the ultrathin 2D δ-MnO2 nanosheet shell creates more reactive active sites. The synergistic effects of different dimensions also contribute to the superior rate capability.

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Lithium cathode materials have been considered as promising candidates for energy storage applications because of their high power/energy densities, low cost, and low toxicity. However, the Li/Ni cation mixing limits their application as practical electrode materials. The cation mixing of lithium transition-metal oxides, which was first considered only as the origin of performance degeneration, has recently been reconsidered as a way to stabilize the structure of active materials. Here we find that as the duration of the post-synthesis thermal treatment (at 500 °C) of LiNiCoMnO (NCM) was increased, the Li/Ni molar ratio in the final product was found to decrease, and this was attributed to the reduction in nickel occupying lithium sites; the cation mixing subtly changed; and those subtle variations remarkably influence their cycling performance. The cathode material with appropriate cation mixing exhibits a much slower voltage decay and capacity fade during long-term cycling. Combining X-ray diffraction, Rietveld analysis, the Fourier transform infrared technique, field-emission scanning electron microscopy, and electrochemical measurements, we demonstrate that an optimal degree of Ni occupancy in the lithium layer enhances the electrochemical performance of layered NMC materials and that this occurs through a "pillaring" effect. The results provide new insights into "cation mixing" as a new concept for material design utilization of layered cathodes for lithium-ion batteries, thereby promoting their further application in lithium-ion batteries with new functions and properties.

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Olivine LiFePO4 with nanoplate, rectangular prism nanorod and hexagonal prism nanorod morphologies with a short b-axis were successfully synthesized by a solvothermal in glycerol and water system. The influences of solvent composition on the morphological transformation and electrochemical performances of olivine LiFePO4 are systematically investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and galvanostatic charge-discharge tests. It is found that with increasing water content in solvent, the LiFePO4 nanoplates gradually transform into hexagonal prism nanorods that are similar to the thermodynamic equilibrium shape of the LiFePO4 crystal. This indicates that water plays an important role in the morphology transformation of the olivine LiFePO4. The electrochemical performances vary significantly with the particle morphology. The LiFePO4 rectangular prism nanorods (formed in a glycerol-to-water ratio of 1:1) exhibit superior electrochemical properties compared with the other morphological particles because of their moderate size and shorter Li(+) ion diffusion length along the [010] direction. The initial discharge capacity of the LiFePO4@C with a rectangular prism nanorod morphology reaches to 163.8 mAh g(-1) at 0.2 C and over 75 mAh g(-1) at the high discharging rate of 20 C, maintaining good stability at each discharging rate.