Enhanced electrode kinetics and electrochemical properties of low-cost NaFe2PO4(SO4)2 via Ca2+ doping as cathode material for sodium-ion batteries

doi:10.1016/j.jmst.2020.10.047

Abstract

Abstract:

In recent years, sodium-ion batteries (SIBs) have been considered as one of the most promising alternatives to lithium-ion batteries (LIBs). Here, a new Na-super-ionic conductor (NASICON) cathode material NaFe₂PO₄(SO₄)₂ is successfully prepared through solid state method for SIBs. While the poor electronic conductivity of iron-based materials results in its poor rate and cycle performance. Then the electrochemical is effectively promoting via Ca²⁺ doping. Na_0.84Ca_0.08Fe₂PO₄(SO₄)₂ have achieved considerable electrochemical properties. The first discharge specific capacity is 121.6mA h g^-1 at 25mA g^-1 with the voltage platform (3.1 V) corresponding to Fe^2+/3+. After 100 cycles, the capacity retention is 55.1 %. The excellent electrochemical performance is caused by some Na⁺ is substituted by Ca²⁺ and leading to the fast sodium kinetics, which is well proved by the powder X-ray diffraction pattern and well corresponding to the galvanostatic intermittent titration technique and cyclic voltammetry testing result (the diffusivity values are around at 10-12cm₂s^-1).

Key words: NaFe₂PO₄(SO₄)₂, Na-super-ionic conductor, Sodium-ion batteries, Cathode, Ca ²⁺ doping

Shao-Fang Li, Zhen-Yi Gu, Jin-Zhi Guo, Xian-Kun Hou, Xu Yang, Bo Zhao, Xing-Long Wu. Enhanced electrode kinetics and electrochemical properties of low-cost NaFe₂PO₄(SO₄)₂ via Ca²⁺ doping as cathode material for sodium-ion batteries[J]. J. Mater. Sci. Technol., 2021, 78: 176-182.

Figures/Tables 5

Fig. 1. XRD Rietveld refinement plots of (a) NFPS and (b) NFPS-Ca0.08; crystal structure of (c) NFPS and (d) NFPS-Ca0.08.

Fig. 2. SEM images of (a) NFPS, (b) NFPS-Ca0.06, (c) NFPS-Ca0.08, (d) NFPS-Ca0.10 and (e) HR-TEM and (f) TEM images of NFPS-Ca0.08. (g) EDS element analysis of NFPS-Ca0.08.

Fig. 3. (a) GCD curves of Na1-2xCaxFe2PO4(SO4)2 (x=0, 0.06, 0.08 and 0.10) at 25mA g-1; (b) rate performance from current density 25mA g-1 to 500mA g-1; (c) cycle testing of NFPS and NFPS-Ca0.08 at the current density of 50mA g-1.

Fig. 4. CV curves of (a) NFPS and (d) NFPS-Ca0.08 at a sweep rate of 0.1mV s-1; the CV curves of (b) NFPS and (e) NFPS-Ca0.08 at various scan rates of 0.1, 0.15, 0.2, 0.3, 0.4 and 0.5mV s-1; the dependence of current of the peak on the square root of the scan rate (v1/2) for (c) NFPS and (f) NFPS-Ca0.08. The potential range is 2.0-4.4V.

Fig. 5. (a) Representation of τ vs. E profile for a single GITT titration on the charge process; (b) corresponding linear behavior of τ1/2 vs. E; (c) GITT test result showing the DNa+ of charge and discharge process of NFPS and NFPS-Ca0.08.

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Enhanced electrode kinetics and electrochemical properties of low-cost NaFe₂PO₄(SO₄)₂ via Ca²⁺ doping as cathode material for sodium-ion batteries

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