Effect of SO42- Doping on Electrochemical Properties of the Nasicon Li3Fe2(PO4)3 Cathode†

doi:10.7503/cjcu20160452

Abstract

Abstract:

Effect of S $O 4 2 -$ doping on electrochemical properties of the Li₃Fe₂(PO₄)₃ cathode materials was studied. Phase constitutents and electrochemical properties of the Li_3-_xFe₂(PO₄)_3-_x(SO₄)_x(x=00.90) materials were characterized by XRD, charge-discharge technology, cyclic voltammetry and electrochemical impedance spectrum. The results proved that the added S $O 4 2 -$ anions mainly dissolved in the Li₃Fe₂(PO₄)₃ compound, concomitant with the secondary phase, Fe₂O₃. Introduction of the S $O 4 2 -$ anions resulted in a parabolic variation of discharging capacity for the Li₃Fe₂(PO₄)₃ compound, and that the sample with the S $O 4 2 -$ content(x) of 0.60 exhibited the best performance. Its initial discharging capacity was about 111.59 mA·h/g at a rate of 0.5C, and this value was 18. 4% higher than that without any S $O 4 2 -$ . After 60 charge-discharge cycles, its capacity retention was around 96% at a rate of 0.5C. Moreover, 97% of the initial capacity was obtained for this material by gradually increasing discharging rates from 0.5C to 5C, and then decreasing back to 0.5C, together with 10 charging-discharging cycles at each rate. Above-mentioned improvement in electrochemical properties for the S $O 4 2 -$ substituted samples should result from their enhanced redox ability, decreased internal resistance and polarization, and increased Li⁺ diffusion coefficients of the batteries.

Key words: Cathode, Nasicon type Li₃Fe₂(PO₄)₃, S $O 4 2 -$ doping, Electrochemical property

CLC Number:

O646

TrendMD:

ZHANG Bo, HE Jun, HUA Zhengshen, WANG Xin, PENG Huifen. Effect of S $O 4 2 -$ Doping on Electrochemical Properties of the Nasicon Li₃Fe₂(PO₄)₃ Cathode^†[J]. Chem. J. Chinese Universities, 2017, 38(1): 108.

Figures/Tables 9

Fig.1 XRD patterns of the Li3-xFe2(PO4)3-x(SO4)x(x=0—0.90) xerogels heat-treated at 650 ℃

Fig.2 Initial charge-discharge curves at 0.5C(A) and initial discharge capacities at different rates(B) for Li3-xFe2(PO4)3-x(SO4)x (A) x: a, a'. 0; b, b'. 0.30; c, c'. 0.45; d, d'. 0.60; e, e'. 0.75; f, f'. 0.90. (B) x: a. 0; b. 0.30; c. 0.60; d. 0.90; e. Li3Fe2(PO4)3; f. Li2.8Fe1.8Ti0.2(PO4)3.

Fig.3 Initial charge-discharge curves at different rates for the Li3-xFe2(PO4)3-x(SO4)x samples (A) x=0; (B) x=0.60.

Fig.4 Cyclic charge-discharge curves at 0.5C rate(A) and variation of discharge capacity with cycle numbers(B) for Li3-xFe2(PO4)3-x(SO4)x

Fig.5 Cycle performance of Li3-xFe2(PO4)3-x(SO4)x(x=0.60) sample at different discharge rates

Fig.6 XRD patterns of the cathode before and after discharging

Fig.7 CV curves of the Li3-xFe2(PO4)3-x(SO4)x at scan rate of 0.1 mV/s x: a. 0; b. 0.30; c. 0.60; d. 0.90.

Fig.8 AC impedance spectra of the Li3-xFe2(PO4)3-x(SO4)x samples(A) and relationships between Zre and ω-1/2(B)

Table 1 Charge transfer resistance(Rct), Warburg coefficients(σ) and Li+ diffusion coefficients(D) of the Li3-xFe2(PO4)3-x(SO4)x samples

x	R_ct/Ω	σ/(Ω·cm²·s^-1/2)	10¹²D/(cm²·s^-1)	x	R_ct/Ω	σ/(Ω·cm²·s^-1/2)	10¹²D/(cm²·s^-1)
0	196.0	97.8	3.97	0.60	103.6	31.9	37.30
0.30	137.6	50.2	13.90	0.75	127.8	75.8	6.60
0.45	117.7	42.3	21.20	0.90	170.5	84.3	5.34

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Effect of S $O 4 2 -$ Doping on Electrochemical Properties of the Nasicon Li₃Fe₂(PO₄)₃ Cathode^†

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