聚乙二醇为碳源合成0.7LiFePO4ּ0.3Li3V2(PO4)3/C 复合正极材料及性能研究

doi:10.15541/jim20140231

摘要/Abstract

摘要：

以LiOH·H₂O、FeC₂O₄·2H₂O、NH₄VO₃和NH₄H₂PO₄为原料, 分别以不同聚合度的聚乙二醇(PEG-200、PEG-600、PEG-1000、PEG-2000、PEG-6000)为碳源, 通过高温固相法合成0.7LiFePO₄·0.3Li₃V₂(PO₄)₃/C复合正极材料(LFVP/C)。用X射线衍射、拉曼光谱和扫描电镜对材料的结构和形貌进行了表征。充放电测试表明, 在电压范围为2.0~4.3 V 时, PEG-200为碳源的LFVP/C的复合正极材料具有较高的比容量、优良的循环性能和倍率特性。10C条件下其放电容量可以保持120 mAh/g。

关键词: 锂离子电池, LiFePO4, Li3V2(PO4)3, 聚乙二醇, 正极材料

Abstract:

Different molecular weight of polyethylene glycol (PEG), including PEG-200, PEG-600, PEG-1000, PEG-2000 and PEG-6000, were used as carbon sources and reduction agents for preparation of 0.7LiFePO₄?0.3Li₃V₂(PO₄)₃/C composites via spay-drying followed solid-state reaction approach. The structure and morphology of the 0.7LiFePO₄?0.3Li₃V₂(PO₄)₃/C composite samples were characterized by X-ray diffraction(XRD), Raman spectroscope and ﬁeld-emission scanning electron microscope (FE-SEM). The diffraction peaks of the synthesized compound were composed of both orthorhombic LiFePO₄ and monoclinic Li₃V₂(PO₄)₃, indicating the synthesized compound is a mixture phase of LiFePO₄ and Li₃V₂(PO₄)₃. The structure of residual carbon was characterized by Raman spectroscope. A lower intensity ratio of the I_D/I_G band for PEG-200 in Raman spectrum indicated more graphite clusters in the structure of carbon, which would enhance the electronic conductivity of the residual carbon. The composites showed higher discharge capacity, better rate capability and cyclic performance. Even at a high charge-discharge rate of 10C, it still maintained a discharge capacity of 120 mAh/g in the potential range of 2.0-4.3 V.

Key words: Lithium-ion battery, LiFePO4, Li3V2(PO4)3, polyethylene glycol, cathode materials

中图分类号:

TQ174

马平平, 刘志坚, 夏建华, 卢志超. 聚乙二醇为碳源合成0.7LiFePO₄ּ0.3Li₃V₂(PO₄)₃/C 复合正极材料及性能研究[J]. 无机材料学报, 2015, 30(2): 122-128.

MA Ping-Ping, LIU Zhi-Jian, XIA Jian-Hua, LU Zhi-Chao. Electrochemical Performance of 0.7LiFePO₄ּ0.3Li₃V₂(PO₄)₃/C Cathode Materials Using Polyethylene Glycol as Carbon Source[J]. Journal of Inorganic Materials, 2015, 30(2): 122-128.

图/表 10

图 1 用不同碳源制备的前驱体的TG曲线

Fig. 1 TG curves of precursors prepared from different carbon sources (a) PEG-200; (b) PEG-1000; (c) PEG-6000

图 2 用不同碳源制备的LFVP/C样品的XRD图谱

Fig. 2 XRD patterns of LFVP/C compounds prepared with different carbon sources (a) PEG-200; (b) PEG-600; (c) PEG-1000; (d) PEG-2000; (e) PEG-6000

图 3 不同碳源样品的拉曼光谱和拟合结果

Fig. 3 Raman spectra and its fitted result of the products with different carbon sources (a) PEG-200; (b) PEG-600; (c) PEG-1000; (d) PEG-2000; (e) PEG-6000

表 1 不同碳源合成LFVP/C样品的 ID/IG ratio、碳含量和电导率结果

Table 1 Results of ID/IG ratio, carbon content and electronic conductivity of LFVP/C compounds prepared with different carbon sources

Carbon source	Wavenumber/cm^-1		Area/(a.u.)	A_D/A_G	A_sp3/A_sp2	Carbon content	Electrical conductivity/(S?cm^-1)
PEG-200	sp²	1352	70022	1.50	0.07	1.73%	1.89×10^-3
	sp²	1590	46753
	sp³	1150	2035
	sp³	1472	5886
PEG-600	sp²	1354	57547	1.84	0.10	1.59%	1.14×10^-4
	sp²	1596	31336
	sp³	1151	3165
	sp³	1491	5744
PEG-1000	sp²	1357	78754	2.07	0.14	1.81%	2.22×10^-5
	sp²	1599	38080
	sp³	1139	6453
	sp³	1504	10158
PEG-2000	sp²	1358	56532	2.17	0.21	1.47%	8.66×10^-5
	sp²	1604	26020
	sp³	1156	6771
	sp³	1508	10759
PEG-6000	sp²	1354	30012	2.68	2.01	1.68%	1.17×10^-5
	sp²	1607	11208
	sp³	1349	57748
	sp³	1558	27004

图4 不同碳源合成LFVP/C样品的扫描电镜照片

Fig. 4 SEM images of LFVP/C compounds prepared with different carbon sources (a) PEG-200; (b) PEG-600; (c) PEG-1000; (d) PEG-2000; (e) PEG-6000

图5 不同碳源合成LFVP/C样品的透射电镜照片

Fig. 5 TEM images of LFVP/C compounds prepared with different carbon sources (a) PEG-200; (b) PEG-600; (c) PEG-1000; (d) PEG-2000; (e) PEG-6000

图6 不同碳源合成样品在不同倍率下的充放电曲线

Fig. 6 Charge-discharge curves of LFVP/C compounds prepared with different carbon sources at different rates (a) 2C; (b) 1C; (c) 5C; (d) 10C

表 2 不同碳源LFVP/C样品放电容量(mAh/g)对比

Table 2 Comparison of discharge capability (mAh/g) of LFVP/C compounds prepared with different carbon sources

Carbon source	0.2C	1C	5C	10C
PEG-200	134	134	126	120
PEG-600	142	138	130	112
PEG-1000	145	139	126	79
PEG-2000	142	141	132	95
PEG-6000	140	141	129	72

图 7 不同碳源样品在不同倍率下循环性能曲线

Fig. 7 Cycle life of LFVP/C compounds prepared with different carbon sources at different rates

图 8 不同碳源样品循环伏安曲线(a)和交流阻抗图(b)

Fig. 8 CV curves (a) and impedance spectra (b) of LFVP/C compounds prepared with different carbon sources at 0.1 mV/s

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聚乙二醇为碳源合成0.7LiFePO₄ּ0.3Li₃V₂(PO₄)₃/C 复合正极材料及性能研究

Electrochemical Performance of 0.7LiFePO₄ּ0.3Li₃V₂(PO₄)₃/C Cathode Materials Using Polyethylene Glycol as Carbon Source

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