Triclinic Off-Stoichiometric Na<inf>3.12</inf>Mn<inf>2.44</inf>(P<inf>2</inf>O<inf>7</inf>)<inf>2</inf>/C Cathode Materials for High-Energy/Power Sodium-Ion Batteries

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Journal Article
ACS Applied Materials and Interfaces, 2018, 10 (29), pp. 24564 - 24572
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© 2018 American Chemical Society. The application of sodium-ion batteries (SIBs) requires a suitable cathode material with low cost, nontoxic, high safety, and high energy density, which is still a big challenge; thus, a basic research on exploring new types of materials is imperative. In this work, a manganic pyrophosphate and carbon compound Na3.12Mn2.44(P2O7)2/C has been synthesized through a feasible sol-gel method. Rietveld refinement reveals that Na3.12Mn2.44(P2O7)2 adopts a triclinic structure (P1 space group), which possesses spacious ion diffusion channels for facile sodium migration. The off-stoichiometric phase is able to offer more reversible Na+, delivering an enhanced reversible capacity of 114 mA h g-1 at 0.1 C, and because of the strong "inductive effect" that (P2O7)4- groups imposing on the Mn3+/Mn2+ redox couple, Na3.12Mn2.44(P2O7)2/C presents high platforms above 3.6 V, contributing a remarkable energy density of 376 W h kg-1, which is among the highest Fe-/Mn-based polyanion-type cathode materials. Furthermore, the off-stoichiometric compound also presents satisfactory rate capability and long-cycle stability, with a capacity retention of 75% after 500 cycles at 5 C. Ex situ X-ray diffraction demonstrates a single-phase reaction mechanism, and the density functional theory calculations display two one-dimensional sodium migration paths with low energy barriers in Na3.12Mn2.44(P2O7)2, which is vital for the facile sodium storage. We believe that this compound will be a competitive cathode material for large-scale SIBs.
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