Cr 3+掺杂LiSn2(PO4)3负极材料的电化学性能研究

doi:10.15541/jim20180279

摘要/Abstract

摘要：

利用Cr ³⁺离子对LiSn₂(PO₄)₃化合物中的Sn ⁴⁺进行掺杂。对所制备的材料Li₁₊_xCr_xSn_2-_x(PO₄)₃进行X射线衍射(XRD)测试, 结果表明, 在x=0.1~0.3时可得到单一的α-LiSn₂(PO₄)₃相, 掺杂浓度进一步增加则会导致少量SnO₂第二相的析出。尽管引入Cr不能抑制LiSn₂(PO₄)₃在首次放电过程中分解, 但x=0.3的样品电化学性能得到显著改善。电池在100和800 mA/g电流密度下25次充放电循环后放电容量分别为403.1和241.9 mAh/g, 并具有较好的循环性能和倍率性能。导致上述结果的主要原因是Li₃PO₄和Cr复合基体的空间效应, 有效避免了Sn颗粒在充放电循环中的团聚, 改善了电化学反应环境, 从而提高了Sn颗粒的利用效率。

关键词: 锡基材料, 负极材料, LiSn₂(PO₄)₃, Cr ³⁺掺杂, 电化学性能

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

中图分类号:

TQ136

冯晓晶, 王恭凯, 王晓然, 何珺, 王新, 彭会芬. Cr ³⁺掺杂LiSn₂(PO₄)₃负极材料的电化学性能研究[J]. 无机材料学报, 2019, 34(4): 358-364.

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.

图/表 9

图1 Cr3+掺杂浓度为0.4的样品于不同温度热处理的XRD图谱(a)及100 mA/g电流密度下的第二次充放电曲线(b)

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

图2 成份为Li1+xCrxSn2-x(PO4)3 (x=0~0.5)的干凝胶于不同温度热处理的XRD图谱

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)

图S1 Li1+xCrxSn2-x(PO4)3样品的SEM照片和EDX图谱

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

图S2 Li1+xCrxSn2-x(PO4)3 (x=0, 0.2, 0.3, 0.4)样品的XPS图谱

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

图3 对应图2中(x=0, 650 ℃以及x=0.1~0.5, 900 ℃)各样品装配成的电池在100 mA/g电流密度下的第二次充放电曲线(a), 不同电流密度下的放电容量(b)及Li1Sn2(PO4)3 (c), Li1.3Cr0.3Sn1.7(PO4)3 (d)的充放电曲线

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)

图4 Li1.3Cr0.3Sn1.7(PO4)3样品装配的电池在100 mA/g电流密度下不同循环的充放电曲线(a), 不同电流密度下样品装配的电池放电容量的变化(b)及在100~800 mA/g范围内的变倍率性能(c)

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)

图5 不同浓度Cr3+掺杂样品的交流阻抗谱(a)和实部Z°与ω-1/2的关系(b), 插图为(a)的局部放大及等效电路图

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

表1 根据图5计算各样品的电荷转移阻抗Rct、Warburg系数σ及Li+扩散系数D

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

图S3 Li1.3Cr0.3Sn1.7(PO4)3充放电至不同电压产物的XRD图谱(a)及对图S3 (a)方框区域的放大图谱(b)

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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Cr ³⁺掺杂LiSn₂(PO₄)₃负极材料的电化学性能研究

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

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