Abstract

Nanocrystalline NaMn2O4 with a crystallite size of ∼8–10 nm exhibiting a new close packed hexagonal crystalline form, different from the known stable orthorhombic (Pbam or Pmnm symmetry) or monoclinic structures common to the Na–Mn–O system, has been synthesized by a high energy mechano-chemical milling process (HEMM) using Na2O2 and Mn2O3 as starting materials. The newly synthesized structure of NaMn2O4 has been studied as a cathode for sodium ion rechargeable batteries. The HEMM derived NaMn2O4 shows a 1st cycle discharge capacity ∼75 mAh/g, ∼86 mAh/g and ∼95 mAh/g when cycled at a rate of ∼40 mA/g in the potential window ∼2.0–4.0 V, ∼2–4.2 V and ∼2–4.5 V, respectively. The nanostructured NaMn2O4 shows a fade in capacity of 0.3% per cycle and a moderate rate capability when cycled in the potential window 2–4 V. However, electrolyte decomposition occurring during charging of the electrode above ∼3.8 V needs to be resolved in order utilize the full capacity of NaMn2O4 as well as improve the stability of the electrode.

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