High voltage cathode materials Li-excess layered oxide compounds Li[Ni x Li 1/3À2x/3 Mn 2/3Àx/3 ]O 2 (0 < x < 1/2) are investigated in a joint study combining both computational and experimental methods. The bulk and surface structures of pristine and cycled samples of Li[Ni 1/5 Li 1/5 Mn 3/5 ]O 2 are characterized by synchrotron X-Ray diffraction together with aberration corrected Scanning Transmission Electron Microscopy (a-S/TEM). Electron Energy Loss Spectroscopy (EELS) is carried out to investigate the surface changes of the samples before/after electrochemical cycling. Combining first principles computational investigation with our experimental observations, a detailed lithium de-intercalation mechanism is proposed for this family of Li-excess layered oxides. The most striking characteristics in these high voltage high energy density cathode materials are 1) formation of tetrahedral lithium ions at voltage less than 4.45 V and 2) the transition metal (TM) ions migration leading to phase transformation on the surface of the materials. We show clear evidence of a new spinel-like solid phase formed on the surface of the electrode materials after high-voltage cycling. It is proposed that such surface phase transformation is one of the factors contributing to the first cycle irreversible capacity and the main reason for the intrinsic poor rate capability of these materials.

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Large-aspect-ratio composite nanofibers with interior hierarchical interfaces are employed to break the adverse coupling of electric displacement and breakdown strength in flexible poly(vinylidene fluoride-hexafluoropropylene) nanocomposite films, a small loading of 3 vol% BaTiO3@TiO2 nanofibers gives rise to the highestenergy density (≈31.2 J cm(-3)) ever achieved in polymer nanocomposites dielectrics.

A novel oxygen vacancy assisted transition metal (TM) diffusion mechanism is proposed for the first time to explain the near-surface phase transformation in lithium excess transition metal layered oxides. Oxygen vacancies and TM migration have been observed at nm scale spatial resolution by Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy. Formation of (dilute) oxygen vacancies and their roles in assisting transition metal ion diffusion were further investigated using first principles calculations. The activation barriers of TM diffusion in the presence of oxygen vacancies are drastically reduced and consistently in a reasonable range for room temperature diffusion.

First-principles calculations are performed to study the electronic properties and Li storage capability of V2C and its corresponding fluoride and hydroxide. We find that the V2C monolayer is metallic with antiferromagnetic configuration, while its derived V2CF2 and V2C(OH)2 in their the most stable configurations are small-gap antiferromagnetic semiconductors. Li adsorption could enhance the electric conductivity of V2C fluoride and hydroxide. The bare V2C monolayer shows fast Li diffusion with low diffusion barrier height and very high Li storage capacity (with theoretical value ∼940 mAh/g), while the passivated F or OH atoms on its surface tend to impede Li diffusion and largely reduce the Li storage capacity. Moreover, the average intercalation potentials for V2C-based materials are calculated to be relatively low. Our results suggest that V2C monolayer could be a promising anode material for Li-ion batteries.

We report on layered NaTiO2as a potential anode material for Na-ion batteries.

Searching for suitable anodes with good performance is a key challenge for rechargeable Na-ion batteries (NIBs). Using the first-principles method, we predict that 2D nitrogen electride materials can be served as anode materials for NIBs. Particularly, we show that Ca2N meets almost all the requirements of a good NIB anode. Each formula unit of a monolayer Ca2N sheet can absorb up to four Na atoms, corresponding to a theoretical specific capacity of 1138 mAh·g(-1). The metallic character for both pristine Ca2N and its Na intercalated state NaxCa2N ensures good electronic conduction. Na diffusion along the 2D monolayer plane can be very fast even at room temperature, with a Na migration energy barrier as small as 0.084 eV. These properties are key to the excellent rate performance of an anode material. The average open-circuit voltage is calculated to be 0.18 V vs Na/Na(+) for the chemical stoichiometry of Na2Ca2N and 0.09 V for Na4Ca2N. The relatively low average open-circuit voltage is beneficial to the overall voltage of the cell. In addition, the 2D monolayers have very small lattice change upon Na intercalation, which ensures a good cycling stability. All these results demonstrate that the Ca2N monolayer could be an excellent anode material for NIBs.

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