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Title: Iron-Doped Sodium Vanadium Oxyflurophosphate Cathodes for Sodium-Ion Batteries—Electrochemical Characterization and In Situ Measurements of Heat Generation

Journal Article · · ACS Applied Materials and Interfaces

Sodium-ion batteries (NaIBs) are increasingly being envisioned for grid-scale energy-storage systems because of cost advantages. However, implementation of this vision has been challenged by the low-energy densities delivered by most NaIB cathodes. Toward addressing this challenge, the authors report the synthesis and characterization of a new iron-doped Na3Fe0.3V1.7O(PO4)2F2 cathode using a novel facile hydrothermal route. The synthesized material was characterized using scanning electron microscopy, X-ray diffraction, and Mössbauer spectroscopy techniques. The obtained discharge capacity in the half-cell configuration lies from 119 to 125 to 130 mA h/g at C/10 while tested using three different electrolyte formulations, dimethyl carbonate–ethylene carbonate (EC)–propylene carbonate (PC), diethyl carbonate–EC, and EC–PC, respectively. The synthesized cathodes were also evaluated in full-cell configurations, which delivered an initial discharge capacity of 80 mA h/g with NaTi2(PO4)3MWCNT as the anode. Ionic diffusivity and interfacial charge transfer kinetics were also evaluated as a function of temperature and sodium concentration, which revealed that electrochemical rate performances in this material were limited by charge-transfer kinetics. To understand the heat generation mechanism of the Na/Na3Fe0.3V1.7O(PO4)2F2 half-cell during charge and discharge processes, an electrochemical isothermal calorimetry measurement was carried out at different current rates for two different temperatures (25 and 45 °C). The results showed that the amount of heat generated was strongly affected by the operating charge/discharge state, C-rate, and temperature. Altogether, this work provides a new synthesis route for the development of iron-doped Na3Fe0.3V1.7O(PO4)2F2-based high-performance sodium cathode materials aimed at providing a viable pathway for the development and deployment of large-scale energy-storage based on sodium battery systems.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Electricity (OE)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1657957
Journal Information:
ACS Applied Materials and Interfaces, Vol. 12, Issue 37; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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