Ultraporous, Ultrasmall MgMn 2 O 4 Spinel Cathode for a Room-Temperature Magnesium Rechargeable Battery.
Hiroaki KobayashiYu FukumiHiroto WatanabeReona IimuraNaomi NishimuraToshihiko MandaiYoichi TominagaMasanobu NakayamaTetsu IchitsuboItaru HonmaHiroaki ImaiPublished in: ACS nano (2023)
Magnesium rechargeable batteries (MRBs) promise to be the next post lithium-ion batteries that can help meet the increasing demand for high-energy, cost-effective, high-safety energy storage devices. Early prototype MRBs that use molybdenum-sulfide cathodes have low terminal voltages, requiring the development of oxide-based cathodes capable of overcoming the sulfide's low Mg 2+ conductivity. Here, we fabricate an ultraporous (>500 m 2 g -1 ) and ultrasmall (<2.5 nm) cubic spinel MgMn 2 O 4 (MMO) by a freeze-dry assisted room-temperature alcohol reduction process. While the as-fabricated MMO exhibits a discharge capacity of 160 mAh g -1 , the removal of its surface hydroxy groups by heat-treatment activates it without structural change, improving its discharge capacity to 270 mAh g -1 ─the theoretical capacity at room temperature. These results are made possible by the ultraporous, ultrasmall particles that stabilize the metastable cubic spinel phase, promoting both the Mg 2+ insertion/deintercalation in the MMO and the reversible transformation between the cubic spinel and cubic rock-salt phases.