研究快报

碳热还原法制备Zn掺杂的LiFePO4及其电化学性能

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  • (1. 中国科学院 新疆理化技术研究所, 乌鲁木齐830011; 2. 中国科学院 研究生院, 北京100049; 3. 新疆电子信息材料与器件重点实验室,  乌鲁木齐830011)

收稿日期: 2010-02-22

  修回日期: 2010-04-01

  网络出版日期: 2010-07-19

基金资助

Xinjiang High-Technology Research & Development Program (200716117)

Synthesis and Electrochemical Characterizations of Zinc-doped LiFePO4/C by Carbothermal Reduction

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  • (1. Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, China; 2. Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 3. Xinjiang Key Laboratory of Electronic Information Materials and Devices, Urumqi 830011, China)

Received date: 2010-02-22

  Revised date: 2010-04-01

  Online published: 2010-07-19

Supported by

Xinjiang High-Technology Research & Development Program (200716117)

摘要

利用碳热还原法制备了LiFePO4/C 以及 Zn掺杂的 LiFePO4/C. 通过X射线衍射、扫描电镜、透射电镜、恒流充放电、循环伏安法等手段对其物化性质进行了分析. 结果表明: 少量Zn掺杂不改变LiFePO4的晶体结构. 在充放电过程中, Zn2+可以减少晶体体积收缩, 为锂离子的扩散提供较大的空间, 使其充放电性能特别是较高倍率下的循环特性得到提高.

本文引用格式

华 宁, 王辰云, 康雪雅, 吐尔迪, 韩 英 . 碳热还原法制备Zn掺杂的LiFePO4及其电化学性能[J]. 无机材料学报, 2010 , 25(8) : 887 -892 . DOI: 10.3724/SP.J.1077.2010.10105

Abstract

Alien atom doping has been adopted to modify the electrochemical performance of olivine type LiFePO4 for cathode material. Here, we report that zinc-doping can improve the performance of LiFePO4/C immensely by a simple method. LiFePO4/C and Zn-doped LiFePO4/C cathode materials were firstly synthesized by carbothermal reduction method. Physical-chemical characterizations were done by X-ray diffraction, scanning electron microscope and transmittance electron microscope. Electrochemical behavior of the cathode materials were analyzed by using cyclic voltammetry, and galvanostatic measurements were employed to characterize the reaction of lithium ion insertion and de-insertion. ICP and XRD analyses indicate that Zn ions were sufficiently doped in LiFePO4 and did not alter its crystal structure. During de-intercalation and intercalation process of lithium ions, the doped zinc atoms protect the LiFePO4 crystal from shrink. Consequently, the conductivity is enhanced after doping. It is noted that zinc ions doping can improve performance of LiFePO4, especially on the aspect of stable cycle-life at higher C rate.

参考文献

[1]Padhi A K, Nanjundaswamy K S, Goodenough J B. Phospho- olivines as positive-electrode materials for rechargeable lithium batteries.J. Electrochem. Soc,1997, 144(4):1188-1194
[2]Padhi A K, Nanjundaswamy K S, Masquelier C, et al. Effect of structure on the Fe3+/Fe2+ redox couple in iron phosphates.J. Electrochem. Soc,1997, 144(5):1609-1613
[3]Thackeray M. Lithium-ion batteries-an unexpected conductor.Nat. Mater,2002, 1(2):81-82
[4]Higuchi M, Katayama K, Azuma Y, et al. Synthesis of LiFePO4 cathode material by microwave processing.J. Power Sources,2003, 119-121:258-261
[5]Andersson A S, Thomas J O. The source of first-cycle capacity loss in LiFePO4.J. Power Sources,2001, 97-98:498-502
[6]Huang H, Yin S C, Nazar L F. Approaching theoretical capacity of LiFePO4 at room temperature at high rates. Electrochem. Solid State Lett., 2001, 4(10): A170-A172.
[7]Ravet N, Chouinard Y, Magnan J F, et al. Electroactivity of natural and synthetic triphylite.J. Power Sources,2001, 97-98:503-507
[8]Islam M S, Driscoll D J, Fisher C A J, et al. Atomic-scale investigation of defects, dopants, and lithium transport in the LiFePO4 olivine-type battery material.Chem. Mat,2005, 17(20):5085-5092
[9]Delacourt C, Wurm C, Laffont L, et al. Electrochemical and electrical properties of Nb- and/or C-containing LiFePO4 composites.Solid State Ionics,2006, 177(3/4):333-341
[10]Kang H C, Jun D K, Jin B, et al. Optimized solid-state synthesis of LiFePO4 cathode materials using ball-milling.J. Power Sources,2008, 179(1):340-346
[11]Franger S, Benoit C, Bourbon C, et al. Chemistry and electrochemistry of composite LiFePO4 materials for secondary lithium batteries.J. Phys. Chem. Solids,2006, 67(5/6):1338-1342
[12]Herle P S, Ellis B, Coombs N, et al. Nano-network electronic conduction in iron and nickel olivine phosphates.Nat. Mater,2004, 3(3):147-152
[13]Rho Y H, Nazar L F, Perry L, et al. Surface chemistry of LiFePO4 studied by mossbauer and X-ray photoelectron spectroscopy and its effect on electrochemical properties. J. Electrochem. Soc., 2007, 154(4): A283-A289.
[14]Hu Y Q, Doeff M M, Kostecki R, et al. Electrochemical performance of Sol-Gel synthesized LiFePO4 in lithium batteries. J. Electrochem. Soc., 2004, 151(8): A1279-A1285.
[15]Meligrana G, Gerbaldi C, Tuel A, et al. Hydrothermal synthesis of high surface LiFePO4 powders as cathode for Li-ion cells.J. Power Sources,2006, 160(1):516-522
[16]Zhu B Q, Li X H, Wang Z X, et al. Novel synthesis of LiFePO4 by aqueous precipitation and carbothermal reduction.Mater. Chem. Phys,2006, 98(2/3):373-376
[17]Barker J, Saidi M Y, Swoyer J L. Lithium iron(II) phospho-olivines prepared by a novel carbothermal reduction method. Electrochem. Solid State lett., 2003, 6(3): A53-A55.
[18]Mi C H, Cao G S, Zhao X B. Low-cost, one-step process for synthesis of carbon-coated LiFePO4 cathode.Mater. Lett,2005, 59(1):127-130
[19]Chung S Y, Bloking J T, Chiang Y M. Electronically conductive phospho-olivines as lithium storage electrodes.Nat. Mater,2002, 1(2):123-128
[20]Liu H, Cao Q, Fu L J, et al. Doping effects of zinc on LiFePO4 cathode material for lithium ion batteries.Electrochemistry Communications,2006, 8(10):1553-1557
[21]Shenouda A Y, Liu H K. Studies on electrochemical behaviour of zinc-doped LiFePO4 for lithium battery positive electrode.J. Alloys Compd,2009, 477(1/2):498-503
[22]Ravet N, Gauthier M, Zaghib K, et al. Mechanism of the Fe3+ reduction at low temperature for LiFePO4 synthesis from a polymeric additive.Chem. Mat,2007, 19(10):2595-2602
[23]Meethong N, Kao Y H, Speakman S A, et al. Aliovalent substitutions in olivine lithium iron phosphate and impact on structure and properties.Adv. Funct. Mater,2009, 19(7):1060-1070
[24]Moskon J, Dominko R, Cerc-Korosec R, et al. Morphology and electrical properties of conductive carbon coatings for cathode materials.J. Power Sources,2007, 174(2):683-688

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