Electrochemical properties and evolution of the phase transformation behavior in the NASICON-type Na3+xMnxV2-x(PO4)3 (0≤x≤1) cathodes for Na-ion batteries

Maxim V. Zakharkin, Oleg A. Drozhzhin, Sergey V. Ryazantsev, Dmitry Chernyshov, Maria A. Kirsanova, Ivan V. Mikheev, Egor M. Pazhetnov, Evgeny V. Antipov, Keith J. Stevenson

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

NASICON-structured cathode materials are considered as possible candidates for high-performance Na-ion batteries. Further increase of energy density of the Na3V2(PO4)3 may be achieved by substitution of the V cations by other transition metals. Here, we show that a family of Na3+xMnxV2-x(PO4)3 (0≤x≤1, Δx=0.2) cathode materials demonstrates remarkable diversity of the electrochemical properties and phase transformations depending on degree of substitution and cut-off voltage. An intermediate “Na2M2(PO4)3” phase was found for all compounds studied by means of operando powder X-ray diffraction. When Mn content is low (x~0–0.4), it coexists with Na3+xMnxV2-x(PO4)3 or Na1+xMnxV2-x(PO4)3. Increase in Mn content extends the length of the solid solution region corresponding to sodiated, intermediate and desodiated phases. All Mn-substituted samples are characterized by additional high-voltage plateau (~3.9 V) at charge-discharge curves. Na3+xMnxV2-x(PO4)3 (x≥0.4) compositions exhibit 8–10% energy density gain in comparison to Na3V2(PO4)3 material, Na3.2Mn0.2V1.8(PO4)3 and Na3.4Mn0.4V1.6(PO4)3 are most preferable in terms of cycling stability.

Original languageEnglish
Article number228231
JournalJournal of Power Sources
Volume470
DOIs
Publication statusPublished - 15 Sep 2020

Keywords

  • Cathode material
  • NaMnV(PO)
  • NASICON
  • Operando XRD
  • Phase transitions
  • Sodium-ion battery

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