Rechargeable magnesium batteries have lately received great attention for large-scale energy storage systems due to their high volumetric capacities, low materials cost, and safe characteristic. However, the bivalency of Mg(2+) ions has made it challenging to find cathode materials operating at high voltages with decent (de)intercalation kinetics. In an effort to overcome this challenge, we adopt an unconventional approach of engaging crystal water in the layered structure of Birnessite MnO2 because the crystal water can effectively screen electrostatic interactions between Mg(2+) ions and the host anions. The crucial role of the crystal water was revealed by directly visualizing its presence and dynamic rearrangement using scanning transmission electron microscopy (STEM). Moreover, the importance of lowering desolvation energy penalty at the cathode-electrolyte interface was elucidated by working with water containing nonaqueous electrolytes. In aqueous electrolytes, the decreased interfacial energy penalty by hydration of Mg(2+) allows Birnessite MnO2 to achieve a large reversible capacity (231.1 mAh g(-1)) at high operating voltage (2.8 V vs Mg/Mg(2+)) with excellent cycle life (62.5% retention after 10000 cycles), unveiling the importance of effective charge shielding in the host and facile Mg(2+) ions transfer through the cathode's interface.

All-solid-state batteries incorporating lithium metal anode have the potential to address the energy density issues of conventional lithium-ion batteries that use flammable organic liquid electrolytes and low-capacity carbonaceous anodes. However, they suffer from high lithium ion transfer resistance, mainly due to the instability of the solid electrolytes against lithium metal, limiting their use in practical cells. Here, we report a complex hydride lithium superionic conductor, 0.7Li(CB 9 H 10 )–0.3Li(CB 11 H 12 ), with excellent stability against lithium metal and a high conductivity of 6.7 × 10 −3 S cm −1 at 25 °C. This complex hydride exhibits stable lithium plating/stripping reaction with negligible interfacial resistance (<1 Ω cm 2 ) at 0.2 mA cm −2 , enabling all-solid-state lithium-sulfur batteries with high energy density (>2500 Wh kg −1 ) at a high current density of 5016 mA g −1 . The present study opens up an unexplored research area in the field of solid electrolyte materials, contributing to the development of high-energy-density batteries.

Li and Mn‐rich layered cathodes, despite their high specific capacity, suffer from capacity fading and discharge voltage decay upon cycling. Both specific capacity and discharge voltage of Li and Mn‐rich cathodes are stabilized upon cycling by optimized Al doping. Doping Li and Mn‐rich cathode materials Li1.2Ni0.16Mn0.56Co0.08O2 by Al on the account of manganese (as reflected by their stoichiometry) results in a decrease in their specific capacity but increases pronouncedly their stability upon cycling. Li1.2Ni0.16Mn0.51Al0.05Co0.08O2 exhibits 96% capacity retention as compared to 68% capacity retention for Li1.2Ni0.16Mn0.56Co0.08O2 after 100 cycles. This doping also reduces the decrease in the average discharge voltage upon cycling, which is the longstanding fatal drawback of these Li and Mn‐rich cathode materials. The electrochemical impedance study indicates that doping by Al has a surface stabilization effect on these cathode materials. The structural analysis of cycled electrodes by Raman spectroscopy suggests that Al doping also has a bulk stabilizing effect on the layered LiMO2 phase resulting in the better electrochemical performance of Al doped cathode materials as compared to the undoped counterpart. Results from a prolonged systematic work on these cathode materials are presented and the best results that have ever been obtained are reported.

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Layered transition metal oxides are considered promising cathodes for sodium ion batteries (SIBs) due to their superior specific capacities. However, they usually suffer from insufficient cycling and rate performance mainly from the structural instability during repeated cycles. We overcome these longstanding challenges by engaging crystal water in the interlayer space of sodium manganese oxide under the Birnessite framework. The crystal water enhances Na ion diffusion both in the crystal host and at the interface, suppresses fatal Mn2+ dissolution, and improves long-term structural stability, leading to excellent performance in rate capability and cycle life. The current study suggests that many hydrated materials can be good candidates for electrode materials of emerging rechargeable batteries that need to deal with the large size or multivalent charge of their carrier ions.