富锂正极材料Li1.2Mn0.54Ni0.13Co0.13O2的FePO4包覆研究

doi:10.15541/jim20140268

摘要/Abstract

摘要：

采用碳酸盐共沉淀结合高温固相焙烧法制备了富锂正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂, 并用不同量的FePO₄对其进行表面包覆改性。SEM分析结果显示, FePO₄可以均匀地包覆在富锂材料的颗粒表面, XRD显示包覆后的材料很好地保持了原有的层状结构, 且FePO₄呈非晶态。电化学测试表明改变FePO₄包覆量可以调节该材料特定的电性能指标: FePO₄包覆量为2wt% 的材料具有最大的首次充放电容量, 在0.05C下分别为325.9和258.4 mAh/g; FePO₄包覆量为4wt%的材料兼具较高的放电容量和循环稳定性; 材料的首次充放电效率随着FePO₄含量的增加而逐渐升高, FePO₄包覆量为20wt%时, 首次充放电效率达到97.4%。

关键词: Li1.2Mn0.54Ni0.13Co0.13O2, 碳酸盐共沉淀, FePO4, 表面包覆改性

Abstract:

Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ with a rod-like morphology was prepared by a carbonate co-precipitation method followed by a high-temperature solid state reaction, and coated with different amounts of FePO₄. XRD results and SEM images show that the particles of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ are uniformly coated with amorphous FePO₄. The amorphous FePO₄ layer not only inhibits the reaction between Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ and electrolyte, but also acts as lithium ion receptor during the initial charging process. So, the surface modification of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ with FePO₄ reduces the initial irreversible capacity loss, and improves cyclic and rate performance. Specific electrochemical performance can be achieved by adjusting the amount of FePO₄. Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ coated with 2wt% FePO₄ exhibits the highest initial charge and discharge capacity, 325.9 and 258.4 mAh/g at 0.05C rate, respectively. The material coated with 4wt% FePO₄ shows high discharge capacity and good cycle stability. And with the increase of FePO₄ amounts, the initial coulombic efficiency increases greatly, reaching 97.4% for the sample coated with 20wt% FePO₄.

Key words: Li1.2Mn0.54Ni0.13Co0.13O2, carbonate co-precipitation, FePO4, surface modification

中图分类号:

TQ152

李中, 洪建和, 何岗, 吕璐. 富锂正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂的FePO₄包覆研究[J]. 无机材料学报, 2015, 30(2): 129-134.

LI Zhong, HONG Jian-He, HE Gang, Lü Lu. Effect of FePO₄ Coating on Performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ as Cathode Material for Li-ion Battery[J]. Journal of Inorganic Materials, 2015, 30(2): 129-134.

图/表 7

图1 Li1.2Mn0.54Ni0.13Co0.13O2材料的XRD图谱

Fig. 1 XRD patterns of pristine and FePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2

图2 Li1.2Mn0.54Ni0.13Co0.13O2材料的SEM照片

Fig. 2 SEM images of pristine and FePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 (a) Pristine; (b) 6wt% FePO4; (c) 10wt% FePO4; (d) 20wt% FePO4

图3 Li1.2Mn0.54Ni0.13Co0.13O2材料在0.05C下首次充放电曲线

Fig. 3 Initial charge/discharge curves of the pristine and FePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 at 0.05C rate

图4 Li1.2Mn0.54Ni0.13Co0.13O2材料的首次充放电容量和不可逆容量损失

Fig. 4 Initial charge/discharge capacity and irreversible capacity loss of the pristine and FePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2

图5 Li1.2Mn0.54Ni0.13Co0.13O2材料在0.5C倍率下的循环性能

Fig. 5 Cyclic performance of pristine and FePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 at 0.5C rate

图6 Li1.2Mn0.54Ni0.13Co0.13O2材料的倍率性能

Fig. 6 Rate capability of pristine and FePO4-coated Li1.2Mn0.54 Ni0.13Co0.13O2

图7 Li1.2Mn0.54Ni0.13Co0.13O2材料所组装的半电池的交流阻抗谱

Fig. 7 Electrochemical impedance spectra (EIS) of pristine and FePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2

参考文献 23

[1]	LIU J, WEN Z Y, WU M M, et al.Progress on studies of the cathode materials for Li-ion batteries.Journal of Inorganic Materials, 2002, 17(1): 1-9.
[2]	THACKERAY M M, KAND S H, JOHNSON C S, et al.Li2MnO3-stabilized LiMO2 (M=Mn, Ni, Co) electrodes for lithium-ion batteries.J. Mater. Chem., 2007, 17(30): 3112-3125.
[3]	CONG L N, GAO X G, MA S C, et al.Enhancement of electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 by surface modification with Li4Ti5O12.Electrochim. Acta, 2014, 115: 399-406.
[4]	ZHAO Y J, FENG H L, ZHAO C S, et al.Progress of research on the Li-rich cathode materials xLi2MnO3·(1-x) LiMO2 (M=Co, Fe, Ni1/2Mn1/2…) for Li-ion batteries.Journal of Inorganic Materials, 2011, 26(7): 673-679.
[5]	JOHNSON C S, KIM J S, LEFIEF C, et al.The significance of the Li2MnO3 component in 'composite' xLi2MnO3·(1-x)LiMn0.5Ni0.5O2 electrodes.Electrochem. Commun., 2004, 6: 1085-1091.
[6]	WANG Q Y, LIU J, MANTHIRAM A, et al.High capacity double-layer surface modified Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode with improved rate capability.J. Mater. Chem., 2009, 19: 4965-4972.
[7]	DU K, HU G R.Review of manganese-based solid solution xLi[Li1/3Mn2/3]O2·(1-x)LiMO2.Chin. Sci. Bull.(Chin. Ver.), 2012, 57(10): 794-804.
[8]	WANG Z Y, LIU E Z, GUO L C, et al.Cycle performance improvement of Li-rich layered cathode material Li[Li0.2Mn0.54 Ni0.13Co0.13]O2 by ZrO2 coating.Surf. Coat. Tech., 2013, 235: 570-576.
[9]	ZHENG J M, LI J, ZHANG Z R, et al.The effects of TiO2 coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery.Solid State Ionics, 2008, 179: 1794-1799.
[10]	ZHENG J M, ZHANG Z R, WU X B, et al.The effects of AlF3 coating on the performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery.J. Electrochem. Soc., 2008, 155(10): A775-A782.
[11]	LIU X Y, LIU J L, HUANG T, et al.CaF2-coated Li1.2Mn0.54 Ni0.13Co0.13O2 as cathode materials for Li-ion batteries.Electrochim. Acta, 2013, 109: 52-58.
[12]	WU Y, MURUGAN A V, MANTHIRAM A.Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes by AlPO4.J. Electrochem. Soc., 2008, 155(9): A635-A641.
[13]	GAO J, MANTHIRAM A.Eliminating the irreversible capacity loss of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode by blending with other lithium insertion hosts.J. Power Sources, 2009, 191(2): 644-647.
[14]	GERBALDI C, MELIGRANA G, BODOARDO S, et al.FePO4 nanoparticles supported on mesoporous SBA-15: Inter esting cathode materials for Li-ion cells . J. Power Sources, 2007, 174(2): 501-507.
[15]	LI G, YANG Z X, YANG W S.Effect of FePO4 coating on electrochemical and safety performance of LiCoO2 as cathode material for Li-ion batteries. J. Power Sources, 2008, 183(2): 741-748.
[16]	LIU X Z, LI H Q, ZHOU H S, et al.Fabrication of FePO4 layer coated LiNi1/3Co1/3Mn1/3O2: towards high-performance cathode materials for lithium ion batteries. Electrochim. Acta, 2012, 83: 253-258.
[17]	WANG Z Y, LIU E Z, HE C N, et al.Effect of amorphous FePO4 coating on structure and electrochemical performance of Li1.2Ni0.13 Co0.13Mn0.54O2 as cathode material for Li-ion batteries.J. Power Sources, 2013, 236: 25-32.
[18]	DENG S N, SHI Z C, ZHENG J, et al.Performance of Li1.2Mn0.54Ni0.13Co0.13O2 as cathode materials for lithium ion batteries by surface coating.Chinese Journal of Power Sources, 2012, 36(4): 463-466.
[19]	ZHENG J M, WU X B, YANG Y.Synthesis optimization, characterization and electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 as cathode material of lithium ion battery.Chinese Journal of Power Sources, 2011, 35(10): 1188-1192.
[20]	QING C B, BAI Y, YANG J M, et al.Enhanced cycling stability of LiMn2O4 cathode by amorphous FePO4 coating.Electrochim. Acta, 2011, 56(19): 6612-6618.
[21]	HE W, QIAN J F, CAO Y L, et al.Improved electrochemical performances of nanocrystalline Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for Li-ion batteries.RSC Advances, 2012, 2(8): 3423-3429.
[22]	TANG C P, YING J R, JIANG C Y, et al.Research of progress of electrode material FePO4 for lithium ion batteries.The Chinese Journal of Nonferrous Metals, 2005, 15(8): 25-29.
[23]	LIU J, WANG Q Y, MANTHIRAM A, et al.Conductive surface modification with aluminum of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes.J. Phys. Chem. C, 2010, 114(20): 9528-9533.

富锂正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂的FePO₄包覆研究

Effect of FePO₄ Coating on Performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ as Cathode Material for Li-ion Battery

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 23

相关文章 7

编辑推荐

Metrics

本文评价

[1]	秦显忠, 杨改, 高剑, 蔡飞鹏, 谭春晖. 聚丙烯酰胺改性LiFePO₄/C正极材料的研究[J]. 无机材料学报, 2016, 31(5): 517-522.
[2]	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.
[3]	杨书廷,刘玉霞,尹艳红,王辉,崔成伟. 镁离子掺杂对 LiFePO₄/C电化学性能和结构的影响[J]. 无机材料学报, 2007, 22(4): 627-630.
[4]	刘素琴,龚本利,黄可龙,张戈,李世彩. 新型碳热还原法制备LiFePO₄/C复合材料及其性能研究[J]. 无机材料学报, 2007, 22(2): 283-286.
[5]	邱亚丽,王保峰,杨立. LiFePO₄纳米粉体的还原插锂合成及其电化学性能研究[J]. 无机材料学报, 2007, 22(1): 79-83.
[6]	杨书廷,李廷举. 掺杂基 LiFe_0.99M_0.01PO₄/C的制备及结构与性能的研究[J]. 无机材料学报, 2006, 21(4): 880-884.
[7]	卢俊彪,唐子龙,张中太,沈万慈. LiFePO₄材料的制备与电池性能的研究[J]. 无机材料学报, 2005, 20(3): 666-670.