Preparation and characterization of high-rate and long-cycle LiFePO4/C nanocomposite as cathode material for lithium-ion battery

Olivine LiFePO4/C nanocomposite cathode materials with small-sized particles and a unique electrochemical performance were successfully prepared by a simple solid-state reaction using oxalic acid and citric acid as the chelating reagent and carbon source. The structure and electrochemical properties of the samples were investigated. The results show that LiFePO4/C nanocomposite with oxalic acid (oxalic acid: Fe2+= 0.75:1) and a small quantity of citric acid are single phase and deliver initial discharge capacity of 122.1 mAh/g at 1 C with little capacity loss up to 500 cycles at room temperature. The rate capability and cyclability are also outstanding at elevated temperature. When charged/discharged at 60 °C, this materials present excellent initial discharge capacity of 148.8 mAh/g at 1 C, 128.6 mAh/g at 5 C, and 115.0 mAh/g at 10 C, respectively. The extraordinarily high performance of LiFePO4/C cathode materials can be exploited suitably for practical lithium-ion batteries.

[1]  Margret Wohlfahrt-Mehrens,et al.  Fine-particle lithium iron phosphate LiFePO4 synthesized by a new low-cost aqueous precipitation technique , 2003 .

[2]  Zhixing Wang,et al.  Synthesis and electrochemical properties of olivine LiFePO4 prepared by a carbothermal reduction method , 2008 .

[3]  J. Apt,et al.  Lithium-ion battery cell degradation resulting from realistic vehicle and vehicle-to-grid utilization , 2010 .

[4]  X. Geng,et al.  In situ growth of LiFePO4 nanorod arrays under hydrothermal condition , 2010 .

[5]  Yun‐Sung Lee,et al.  Synthesis of LiFePO4 Material with Improved Cycling Performance under Harsh Conditions , 2008 .

[6]  U. Starke,et al.  Silicon‐Doped LiFePO4 Single Crystals: Growth, Conductivity Behavior, and Diffusivity , 2009 .

[7]  H. Ahn,et al.  Effect of synthetic conditions on the electrochemical properties of LiMn0.4Fe0.6PO4/C synthesized by sol–gel technique , 2009 .

[8]  Robert Kostecki,et al.  Electrochemical performance of Sol-Gel synthesized LiFePO{sub 4} in lithium batteries , 2004 .

[9]  Yudai Huang,et al.  Preparation and characterization of nano-sized LiFePO4 by low heating solid-state coordination method and microwave heating , 2007 .

[10]  I. Taniguchi,et al.  Synthesis of carbon-coated LiFePO4 nanoparticles with high rate performance in lithium secondary batteries , 2010 .

[11]  Jiulin Wang,et al.  High‐Rate LiFePO4 Electrode Material Synthesized by a Novel Route from FePO4 · 4H2O , 2006 .

[12]  Zaiping Guo,et al.  Synthesis and electrochemical properties of nanosized carbon-coated Li1−3xLaxFePO4 composites , 2010 .

[13]  Rongshun Wang,et al.  Long-term cyclability of LiFePO4/carbon composite cathode material for lithium-ion battery applications , 2009 .

[14]  Zhong-Min Su,et al.  Optimized LiFePO4–Polyacene Cathode Material for Lithium‐Ion Batteries , 2006 .

[15]  Yet-Ming Chiang,et al.  Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties , 2009 .

[16]  Jiajun Chen,et al.  Hydrothermal synthesis of lithium iron phosphate , 2006 .

[17]  H. Jang,et al.  Electrochemical properties of carbon-coated LiFePO4 cathode using graphite, carbon black, and acetylene black , 2006 .

[18]  C. Delmas,et al.  Electrochemical performances in temperature for a C-containing LiFePO4 composite synthesized at high temperature , 2008 .

[19]  I. Willner,et al.  Cover Picture: Increasing the Complexity of Periodic Protein Nanostructures by the Rolling‐Circle‐Amplified Synthesis of Aptamers (Angew. Chem. Int. Ed. 1/2008) , 2008 .

[20]  F. Gao,et al.  Kinetic behavior of LiFePO4/C cathode material for lithium-ion batteries , 2008 .

[21]  H. Pan,et al.  Effects of carbon coating and iron phosphides on the electrochemical properties of LiFePO4/C , 2008 .

[22]  Shin Fujitani,et al.  Study of LiFePO4 by Cyclic Voltammetry , 2007 .

[23]  Bingqing Wei,et al.  Long‐Cycle Electrochemical Behavior of Multiwall Carbon Nanotubes Synthesized on Stainless Steel in Li Ion Batteries , 2009 .

[24]  Yong Zhang,et al.  One-step microwave synthesis and characterization of carbon-modified nanocrystalline LiFePO4 , 2009 .

[25]  Yi-Ping Chiang,et al.  Electrochemical properties of LiFe0.9Mg0.1PO4 / carbon cathode materials prepared by ultrasonic spray pyrolysis , 2007 .

[26]  B. Zhu,et al.  Novel synthesis of LiFePO4 by aqueous precipitation and carbothermal reduction , 2006 .

[27]  L. Nazar,et al.  Nano-network electronic conduction in iron and nickel olivine phosphates , 2004, Nature materials.

[28]  J. Schoonman,et al.  Citric acid-assisted synthesis and characterization of doped LiCoVO4 , 2004 .

[29]  D. Xia,et al.  Synthesises, characterizations and electrochemical properties of spherical-like LiFePO4 by hydrothermal method , 2008 .

[30]  Yet-Ming Chiang,et al.  Electronically conductive phospho-olivines as lithium storage electrodes , 2002, Nature materials.

[31]  C. Cao,et al.  Enhanced electrochemical performance of carbon nanospheres–LiFePO4 composite by PEG based sol–gel synthesis , 2010 .

[32]  Linda F. Nazar,et al.  Synthesis of nanocrystals and morphology control of hydrothermally prepared LiFePO4 , 2007 .

[33]  John O. Thomas,et al.  The source of first-cycle capacity loss in LiFePO4 , 2001 .

[34]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[35]  Byoungwoo Kang,et al.  Battery materials for ultrafast charging and discharging , 2009, Nature.

[36]  Fei Gao,et al.  Preparation and characterization of nano-particle LiFePO4 and LiFePO4/C by spray-drying and post-annealing method , 2007 .

[37]  Zhixing Wang,et al.  Stable cycle-life properties of Ti-doped LiFePO4 compounds synthesized by co-precipitation and normal temperature reduction method , 2009 .

[38]  Q. Lai,et al.  Synthesis by citric acid sol–gel method and electrochemical properties of Li4Ti5O12 anode material for lithium-ion battery , 2005 .

[39]  Zhixing Wang,et al.  LiFePO4 with enhanced performance synthesized by a novel synthetic route , 2008 .

[40]  Ketack Kim,et al.  Effects of organic acids as reducing agents in the synthesis of LiFePO4 , 2010 .

[41]  Rongshun Wang,et al.  An effective and simple way to synthesize LiFePO4/C composite , 2009 .

[42]  C. Chen,et al.  Synthesis and characterization of carbon-coated Li3V2(PO4)3 cathode materials with different carbon sources , 2009 .

[43]  Wanxi Zhang,et al.  Effect of different carbon conductive additives on electrochemical properties of LiFePO4-C/Li batteries , 2008 .

[44]  A. Yamada,et al.  Phase Diagram of Li x ( Mn y Fe1 − y ) PO 4 ( 0 ⩽ x , y ⩽ 1 ) , 2001 .

[45]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[46]  Ilias Belharouak,et al.  High-energy cathode material for long-life and safe lithium batteries. , 2009, Nature materials.