Electrochemical Property of Cr 3+ Doped LiSn2(PO4)3 Anode Material

doi:10.15541/jim20180279

Abstract

Abstract:

Sn ⁴⁺ in the LiSn₂(PO₄)₃ compound was doped with Cr ³⁺ ion. Single phase of α-LiSn₂(PO₄)₃ can be obtained with the Cr ³⁺ contents x=0.1-0.3 for the as-prepared Li₁₊_xCr_xSn_2-_x(PO₄)₃ samples, which were confirmed by X-ray diffraction (XRD) measurement. Further augment of the Cr ³⁺ content led to the precipitation of a little secondary phase such as SnO₂. Although the introduction of Cr could not prevent the LiSn₂(PO₄)₃ from decomposition during initial discharging, the sample with Cr ³⁺ content of 0.3 showed remarkably enhanced electrochemical performances. Specific discharging capacities of 403.1 and 241.9 mAh/g could be delivered at current densities of 100 and 800 mA/g after 25 cycles, respectively. Improvement in electrochemical performance could be attributed to the steric effect of complex matrix composed of Li₃PO₄ and Cr, which was favorable for preventing Sn particles from aggregation during subsequent charge/discharge cycles, Leading to promote utilization efficiency of the precipitated Sn.

Key words: Sn-based materials, anode material, LiSn₂(PO₄)₃, Cr ³⁺ doping, electrochemical properties

CLC Number:

TQ136

Xiao-Jing FENG, Gong-Kai WANG, Xiao-Ran WANG, Jun HE, Xin WANG, Hui-Fen PENG. Electrochemical Property of Cr ³⁺ Doped LiSn₂(PO₄)₃ Anode Material[J]. Journal of Inorganic Materials, 2019, 34(4): 358-364.

Figures/Tables 9

Fig. 1 XRD patterns (a) and the second charge-discharge curves at 100 mA/g (b) of the products heat-treated at various temperatures with Cr3+ content of 0.4

Fig. 2 XRD patterns of the xerogels with Li1+xCrxSn2-x(PO4)3 (x=0-0.5) heat-treated at different temperatures(b) Enlarged patterns of (a)

Fig.S1 SEM images and EDX patterns of the Li1+xCrxSn2-x(PO4)3 samples

Fig.S2 XPS spectra for the Li1+xCrxSn2-x(PO4)3 samples with x of 0.2, 0.3 and 0.4 (a) x=0; (b) x=0.1; (c) x=0.2; (d) x=0.3; (e) x=0.4; (f) x=0.5

Fig. 3 Second charge-discharge curves at 100 mA/g (a) and the discharge capacities at different current densities (b) of the batteries assembled with the samples containing different Cr3+ contents, and the charge-discharge curves at different rates for the samples of Li1Sn2(PO4)3 (c) and Li1.3Cr0.3Sn1.7(PO4)3 (d)

Fig. 4 Cyclic charge-discharge curves at 100 mA/g of the batteries assembled with the sample Li1.3Cr0.3Sn1.7(PO4)3 (a), variation in discharging capacity for the samples of x=0 and x=0.3 (b) and rate performance between 100 mA/g and 800 mA/g for the batteries assembled with the Li1.3Cr0.3Sn1.7(PO4)3 sample (c)

Fig. 5 AC impedance spectra (a) and relationship between Z° and ω-1/2of the samples with different Cr3+ contents (b) with inserts showing local magnification of AC impedance spectra and their equivalent circuit

Table 1 Charge transfer resistance (Rct), Warburg coefficients (σ) in Fig. 5 and Li+ diffusion coefficients (D) of the samples

Cr³⁺content	R_ct/Ω	σ/(Ω·cm²·s^-1/2)	D/(cm²·s^-1)
x=0	563.3	1698.0	2.0×10^-14
x=0.2	260.0	83.4	8.3×10^-12
x=0.3	114.7	32.5	5.5×10^-11
x=0.4	252.2	70.8	1.6×10^-11

Fig.S3 XRD patterns of the Li1.3Cr0.3Sn1.7(PO4)3 electrode after charging and discharging at different voltages (a), and enlargement (b) of the box region in (a)

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Electrochemical Property of Cr ³⁺ Doped LiSn₂(PO₄)₃ Anode Material

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