镁掺杂的非化学计量比磷酸铁锂的制备及性能

doi:10.16085/j.issn.1000-6613.2017-0623

化工进展 ›› 2017, Vol. 36 ›› Issue (08): 3006-3012.DOI: 10.16085/j.issn.1000-6613.2017-0623

镁掺杂的非化学计量比磷酸铁锂的制备及性能

冯颖, 刘凯, 霍涛涛, 张敏卿, Abdul Waqas ANJUM

天津大学化工学院, 天津 300350

收稿日期:2017-04-11 修回日期:2017-04-26 出版日期:2017-08-05 发布日期:2017-08-05
通讯作者: 张敏卿,教授,主要从事过程强化、节能减排等研究。
作者简介:冯颖(1992-),女,硕士研究生,从事锂离子电池正极材料磷酸铁锂研究。E-mail:fengying19920220@163.com。
基金资助:
国家自然科学基金项目（21476158，21621004）。

Synthesis and performance of Mg-doped non-stoichiometric lithium iron phosphate

FENG Ying, LIU Kai, HUO Taotao, ZHANG Minqing, ANJUM Abdul Waqas

School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China

Received:2017-04-11 Revised:2017-04-26 Online:2017-08-05 Published:2017-08-05

摘要/Abstract

摘要： 以Li₂CO₃、FeC₂O₄·2H₂O、MgO、NH₄H₂PO₄为原料，无水葡萄糖为碳源，采用高温固相合成法制备获得4% Mg²⁺掺杂的LiFe_0.96Mg_0.04PO₄/C，并通过分别减少2% Mg²⁺和2% Fe²⁺合成了非化学计量比的LiFe_0.96Mg_0.02PO₄/C和LiFe_0.94Mg_0.04PO₄/C材料。利用X射线衍射（XRD）、X射线光电子能谱（XPS）、红外光谱分析（FTIR）、扫描电镜（SEM）、透射电镜（TEM）表征了Fe²⁺和Mg²⁺含量的变化对材料的物质构成、形貌及结构的影响。通过交流阻抗（EIS）及恒流充放电循环测试对材料的电化学性能进行表征。研究结果表明Mg²⁺均匀地掺入LiFePO₄的晶格中，非化学计量比的LiFe_0.96Mg_0.02PO₄/C和LiFe_0.94Mg_0.04PO₄/C材料的晶胞体积减小，导电性杂质Fe₂P的含量升高，Li-Fe错位现象减少；其中，LiFe_0.94Mg_0.04PO₄/C表现出最优的充放电容量、倍率性能以及循环性能，0.1C、20C倍率下的放电比容量分别为161.2mAh/g、74.7mAh/g，500次循环后20C的容量保持率达到97.3%。

关键词: 磷酸铁锂, 非化学计量比, 电化学, 纳米材料, 合成, 优化

Abstract: LiFe_0.94Mg_0.04PO₄/C, LiFe_0.96Mg_0.02PO₄/C and LiFe_0.96Mg_0.04PO₄/C have been synthesized by a solid-state reaction using Li₂CO₃,FeC₂O₄·2H₂O,MgO,and NH₄H₂PO₄ as starting materials and C₆H₆O₆ as carbon source. X-ray diffraction(XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy(SEM),transmission electron microscopy(TEM)and Fourier transform infrared spectroscopy(FTIR)were used to investigate the effect of Fe²⁺ or Mg²⁺ on the morphology and structure of the prepared materials. The electrochemical performances of different samples were characterized by galvanostatic charge/discharge test and electrochemical impedance spectroscopy(EIS). The results indicated that the crystal lattice parameters and the Li-Fe anti-site defects were reduced, whereas the content of conductive Fe₂P in non-stoichiometric lithium iron phosphate increased when Mg was doped, and LiFe_0.94Mg_0.04PO₄/C exhibited the highest discharge performance, rate capability and excellent cycle performance,whose initial capacities were 161.2mAh/g at 0.1C,and 74.7mAh/g at 20C and the retention rate was 97.3% at 20C after 500 cycles.

Key words: lithium iron phosphate, non-stoichiometric, electrochemistry, nanomaterials, synthesis, optimization

中图分类号:

TM912.9

冯颖, 刘凯, 霍涛涛, 张敏卿, Abdul Waqas ANJUM. 镁掺杂的非化学计量比磷酸铁锂的制备及性能[J]. 化工进展, 2017, 36(08): 3006-3012.

FENG Ying, LIU Kai, HUO Taotao, ZHANG Minqing, ANJUM Abdul Waqas. Synthesis and performance of Mg-doped non-stoichiometric lithium iron phosphate[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 3006-3012.

参考文献

[1] 李雷,杨春,谢晓峰.我国储能产业发展现状、机遇与挑战[J].化工进展,2011,30(s1):748-754. LI L,YANG C,XIE X F.Current situation,opportunities and challenges of energy storage industry in China[J].Chemical Industry and Research Progress,2011,30(s1):748-754.
[2] 张克宇,姚耀春.锂离子电池磷酸铁锂正极材料的研究进展[J].化工进展,2015,34(1):166-172. ZHANG K Y,YAO Y C.Research progress in LiFePO₄ cathode material for lithium-ion batteries[J].Chemical Industry and Research Progress,2015,34(1):166-172.
[3] LIU Y Y,GU J J,ZHANG J L,et al.Controllable synthesis of nano-sized LiFePO₄/C via a high shear mixer facilitated hydrothermal method for high rate Li-ion batteries[J].Electrochimica Acta,2015,173:448-457.
[4] YANG M R,KE W H.The doping effect on the electrochemical properties of LiFe_0.95M_0.05PO₄(M=Mg²⁺,Ni²⁺,Al³⁺ or V³⁺) as cathode materials for lithium-ion cells[J].Journal of the Electrochemical Society,2008,155(10):A729-A732.
[5] ZHANG J L,WANG J,LIU Y Y,et al.High-performance lithium iron phosphate with phosphorus-doped carbon layers for lithium ion batteries[J].Journal of Material Chemistry A,2015,5(3):2043-2049.
[6] 舒进波,张金利,李韡.锰掺杂对于磷酸铁锂高倍率性能影响的研究[J].化工新型材料,2014,42(7):102-104. SHU J B,ZHANG J L,LI W.Efluence of Mn-doping on the high-rate performance of LiFePO₄[J].New Chemical Materials,2014,42(7):102-104.
[7] 唐致远,阮艳莉.新型锂离子电池正极材料的研究进展[J].化工进展,2004,23(8):801-805. TANG Z Y,RUAN Y L.Progress in research of olivine-type cathode material in Li-ion batteries[J].Chemical Industry and Research Progress,2004,23(8):801-805.
[8] 王琦,邓思旭,刘晶冰,等.提高正极材料磷酸铁锂倍率性能的研究进展[J].化工进展,2011,30(12):2652-2657. WANG Q,DENG S X,LIU J B,et al.Research progress in rate performance of LiFePO₄ cathode materials[J].Chemical Industry and Research Progress,2011,30(12):2652-2657.
[9] ÖRNEK A,EFE O. Doping qualifications of LiFe_1-xMg_xPO₄/C nano-scale composite cathode materials[J].Electrochimica Acta,2015,166:338-349.
[10] 李旭,彭文杰,李新海,等.LiFe_1-xMg_xPO₄的制备及其电化学性能[J].中国有色金属学报,2008,18(6):1123-1128. LI X,PENG W J,LI X H,et al.Synthesis and electrochemical properties of LiFe_1-xMg_xPO₄[J].The Chinese Journal of Nonferrous Metals,2008,18(6):1123-1128.
[11] 杨伟,薛建军,陈胜洲,等.Mg²⁺掺杂球形LiFePO₄/C的制备及电池性能[J].华南理工大学学报(自然科学版),2016,44(6):9-13. YANG W,XUE J J,CHEN S Z,et al.Preparation an battery performance of spherical LiFePO₄/C doped with Mg²⁺[J].Journal of South China University of Technology (Natural Science Edition),2016,44(6):9-13.
[12] ISLAM M S,DRISCOLL D J,FISHER C A,et al.Atomic-scale investigation of defects, dopants, and lithium transport in the LiFePO₄ olivine-type battery material[J].Chemistry of Materials,2005,17(20):5085-5092.
[13] PARK K Y,PARK I,KIM H,et al.Lithium-excess olivine electrode for lithium rechargeable batteries[J].Energy & Environmental Science,2016,9:2902-2915.
[14] KANG B,CEDER G.Battery materials for ultrafast charging and discharging[J].Nature,2009,458:190-193.
[15] HU C,YI H,FANG H,et al.Suppressing Li₃PO₄ impurity formation in LiFePO₄/Fe₂P by a nonstoichiometry synthesis and its effect on electrochemical properties[J].Material Letters,2011,65:1323-1326.
[16] HERLE P S,ELLIS B,COOMBS N,et al.Nano-network electronic conduction in iron and nickel olivine phosphates[J].Nature Materials,2004,3:147-152.
[17] AXMANN P,STINNER C,MEHRENS M W,et al. Nonstoichiometric LiFePO₄:defects and related properties[J]. Chemistry of Materials,2009,21(8):1636-1644.
[18] FAN C L,LIN C R,HAN S C,et al.Structure, conductive mechanism and electrochemical performances of LiFePO₄/C doped with Mg²⁺, Cr³⁺ and Ti⁴⁺ by a carbothermal reduction method[J].New Journal of Chemistry,2014,38(2):795-801.
[19] REKLATIS J,DAVIDONIS R,DINDUNE A,et al.Characterization of LiFePO₄/C composite and its thermal stability by Mössbauer and XPS spectroscopy[J].Physical Status Solidi B,2016,253(11):2283-2288.
[20] RHO Y H,NAZAR L F,PERRY L,et al.Surface chemistry of LiFePO₄ studied by Mössbauer and X-ray photoelectron spectroscopy and its effect on electrochemical properties[J]. Journal of Electrochemical Society,2007,154(4):A283-289.
[21] AIT SALAH A,JOZWIAK P,ZAGHIB K,et al.FTIR features of lithium-ion phosphates as electrode materials for rechargeable lithium batteries[J].Spectrochimica Acta Part A,2006,65:1007-1013.
[22] 朱令之,韩恩山,曹吉林,等.改进固相法优化合成碳包覆磷酸亚铁锂正极材料[J].化工进展,2010,29(11):2108-2113. ZHU L Z,HAN E S,CAO J L,et al.An improved solid-state reaction for optimized synthesis of LiFePO₄/C cathode material[J]. Chemical Industry and Research Progress,2010,29(11):2108-2113.
[23] LIU H,LI C,ZHANG H P,et al.Kinetic study on LiFePO₄/C nanocomposites synthesized by solid state technique[J].Journal of Power Sources,2006,159:717-720.

镁掺杂的非化学计量比磷酸铁锂的制备及性能

Synthesis and performance of Mg-doped non-stoichiometric lithium iron phosphate

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