4.8 Article

Na4-M2+/2(P2O7)2 (2/3 7/8, M = Fe, Fe0.5Mn0.5, Mn): A Promising Sodium Ion Cathode for Na-ion Batteries

Journal

ADVANCED ENERGY MATERIALS
Volume 3, Issue 6, Pages 770-776

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/aenm.201200825

Keywords

cathode; Na ion batteries; off-stoichiometry; pyrophosphate; solid solution

Funding

  1. MKE (The Ministry of Knowledge Economy), Korea [NIPA-2012-C1090-1200-0002]
  2. National Research Foundation of Korea (NRF)
  3. Korea Government (MEST) [2011-0027950]
  4. NSERC (Canada)

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A new polyanion-based compound, Na3.12M2.44(P2O7)2 (M = Fe, Fe0.5Mn0.5, Mn) is synthesized and examined as a cathode for Na ion batteries. Off-stoichiometric synthesis induces the formation of a Na-rich phase, Na3.32Fe2.34(P2O7)2 - a member of the solid solution series Na4-Fe2+/2(P2O7)2 (2/3 7/8) - which delivers a reversible capacity of about 85 mA h g-1 at ca. 3 V vs. Na/Na+ and exhibits very stable cycle performance. Above all, it shows fast kinetics for Na ions, delivering an almost constant 72% reversible capacity at rates between C/10 and 10C without the necessity for nanosizing or carbon coating. We attribute this to the spacious channel size along the a-axis, along with a single phase transformation upon de/sodiation.

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