RESUMEN
Spinel-type MgMn2O4 nanoplates â¼10 nm thick were prepared as a positive electrode for magnesium rechargeable batteries by the transformation of metal hydroxide nanoplates. Homogeneous coating with a vanadate layer thinner than 3 nm was achieved on the spinel oxide nanoplates via coverage of the precursor and subsequent mild calcination. We found that the spinel oxide nanoplates with the homogeneous coating exhibit improved electrochemical properties, such as discharge potential, capacity, and cyclability, due to the enhanced insertion and extraction of magnesium ions and suppressed decomposition of electrolytes. The nanometric platy morphology of the spinel oxide and the vanadate coating act synergistically for the improvement of the electrochemical performance.
RESUMEN
To achieve a sustainable-energy society in the future, next-generation highly efficient energy storage technologies, particularly those based on multivalent metal negative electrodes, are urgently required to be developed. Magnesium rechargeable batteries (MRBs) are promising options owing to the many advantageous chemical and electrochemical properties of magnesium. However, the substantially low working voltage of sulfur-based positive electrodes may hinder MRBs in becoming alternatives to current Li-ion batteries. We proposed halide-free noncorrosive ionic liquid-based electrolytes incorporating Mg[TFSA]2 for high-voltage MRB applications. Upon the complexation of Mg[TFSA]2 with tetraglyme (G4) and strict control of the liquid states, the electrolytes achieved excellent anodic stability up to 4.1 V vs. Mg2+/Mg even at 100 °C. The modest electrochemical activities for magnesium deposition/dissolution in the [Mg(G4)][TFSA]2/ionic liquid electrolyte can be improved by certain modifications to the coordination state of [TFSA]-. Dialkyl sulfone was found to be effective in changing the coordination state of [TFSA]- from associated to isolated (free). This coordination change successfully promoted magnesium deposition/dissolution reactions, particularly in the coexistence of ether ligand. By contrast, the coordination of Mg2+ by strongly donating agents such as dimethyl sulfoxide and alkylimidazole led to the complexes inactive electrochemically, suggesting that interaction between Mg2+ and coordination agents predominates the fundamental electrochemical activity. We also demonstrated that an enhancement in the electrochemical activity of electrolytes contributed to improvements in the cycling ability of magnesium batteries with 2.5 V-class MgMn2O4 positive electrodes.
RESUMEN
We demonstrate the oscillatory phenomenon for the twisting growth of a triclinic crystal through in situ observation of the concentration field around the growing tip of a needle by high-resolution phase-shift interferometry.