Abstract
LiFePO4 cathode material was synthesized by CO reducing FePO4 and LiOH precursors.The structure,morphology and electrochemical performances of such LiFePO4 material were characterized by XRD,SEM and charge-discharge tests.It was shown that the particle size of the LiFePO4 synthesized with 5% excess of LiOH in the precursor was about 200 nm.By carbon coating,the LiFePO4 electrode was able to deliver a reversible capacity of 158 mAh·g-1 at 0.1C discharge rate.Temperature-programmed X-ray diffraction was employed to monitor the reaction during the formation of LiFePO4,and Li3Fe2(PO4)3 was found to be an intermediate by analyzing the time-resolved XRD patterns.Kinetic study indicates that nucleation and their growth is the rate-determining step in the process of the reaction and the activation energy of this reaction was 89.44 kJ/mol.
Keywords
LiFePO4, CO reduction, temperature-programmed X-ray diffraction, Li3Fe2(PO4)3, mechanism, kinetics
Publication Date
2008-11-28
Online Available Date
2008-11-28
Revised Date
2008-11-28
Received Date
2008-11-28
Recommended Citation
Yun-hua CHEN, Yong YANG.
Synthesis of the LiFePO_4 by CO Reduction:Reaction Mechanism and Kinetics[J]. Journal of Electrochemistry,
2008
,
14(4): 388-393.
DOI: 10.61558/2993-074X.1927
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol14/iss4/8
References
[1]Padhi A K,Nanjundaswamy K S,Goodenough J B.Phospho-olivines as positive-electrode materials for re-chargeable lithium batteries[J].J Electrochem Soc,1997,144:1188-1194.
[2]Huang H,Yin S C,Nazar L F.Approaching theoreticalcapacity of LiFePO4at room temperature at high rates[J].Electrochem Solid-State Lett,2001,4:A170-A172.
[3]Chen Z,Dahn J R.Reducing carbon in LiFePO4/Ccomposite electrodes to maximize specific energy,volu-metric energy,and tap density[J].J ElectrochemSoc,2002,149:A1184-A1189.
[4]Doeff M,Hu Y,Mclarnon F,et al.Effect of surfacecarbon structure on the electrochemical performance ofLiFePO4[J].Electrochem Solid-State Lett,2003,6:A207-A209.
[5]Shin H C,Cho W I,Jang H.Electrochemical proper-ties of carbon-coated LiFePO4cathode using graphite,carbon black,and acetylene black[J].ElectrochimicaActa,2006,52:1472-1476.
[6]Li X,Kang F,Bai X,et al.A novel network compositecathode of LiFePO4/multiwalled carbon nanotubes withhigh rate capability for lithium ion batteries[J].Elec-trochemistry Communications,2007,9:663-666.
[7]Croce F,Epifanio A D,Hassoun J,et al.A novel con-cept for the synthesis of an improved LiFePO4lithiumbattery cathode[J].Electrochem Solid-State Lett,2002,5:A47-A50.
[8]Park K S,Son J T,Chung H T,et al.Surface modifi-cation by silver coating for improving electrochemicalproperties of LiFePO4[J].Solid State Commun,2004,129:311-314.
[9]Chung S Y,Bloking J T,Chiang Y M.Electronicallyconductive phospho-olivines as lithium storage elec-trodes[J].Nat Mater,2002,2:123-128.
[10]Subramanya Herle P,Ellis B,Coombs N,et al.Nano-network electronic conduction in iron and nickel olivinephosphates[J].Nat Mater,2004,3:147-152.
[11]ZHENG Ming-sen(郑明森),LIU Shan-ke(刘善科),SUN Shi-gang(孙世刚),et al.Cu doping LiFePO4and its electrochemical performance[J].Electrochem-istry(in Chinese),2008,14(1):1-5.
[12]Yamada A,Chung S C,Hinokuma K.OptimizedLiFePO4for lithium battery cathodes[J].J Electro-chem Soc,2001,148:A224-A229.
[13]Takahashi M,Tobishima S,Takei K,et al.Character-ization of LiFePO4as the cathode material for recharge-able lithium batteries[J].J Power Sources,2001,97-98:508-511.
[14]Prosini P P,Zane D,Pasquali M.Improved electro-chemical performance of a LiFePO4-based compositecathode[J].Electrochimica Acta,2001,46:3517-3523.
[15]Shi Zhi-cong(施志聪),Li Chen(李晨),Yang Yong(杨勇).The electrochemical performance studies onnovel LiFePO4cathode materials for Li-ion batteries[J].Electrochemistry(in Chinese),2003,(1):9-14.
[16]Franger S,Cras F L,Bourbon C,et al.LiFePO4syn-thesis routes for enhanced electrochemical performance[J].Electrochem Solid state letter,2002,5:A231-A233.
[17]Kim C W,Lee M H,Jeong W T,et al.Synthesis ofolivine LiFePO4cathode materials by mechanical allo-ying using iron(III)raw material[J].J PowerSources,2005,146:534-538.
[18]Yang J,Xu J J.Nonaqueous Sol-gel synthesis of high-performance LiFePO4[J].Electrochem Solid-StateLett,2004,7:A515-A518.
[19]Wang G X,Bewlay S,Needham S A,et al.Synthesisand characterization of LiFePO4and LiTi0.01Fe0.99PO4cathode materials[J].J Electrochem Soc,2006,153:A25-A31.
[20]Park K S,Kang K T,Lee S B,et al.Synthesis ofLiFePO4with fine particle by co-precipitation method[J].Mater Res Bull,2004,39:1803-1810.
[21]Yang S,Zavalij P Y,Whittingham MS.Hydrothermalsynthesis of lithium iron phosphate cathodes[J].Electrochem Commun,2001,3:505-508.
[22]Shiraishi K,Dokko K,Kanamura K.Formation of im-purities on phospho-olivine LiFePO4during hydrother-mal synthesis[J].J Power Sources,2005,146:555-558.
[23]Barker J,Saidi M Y,Swoyer J L.Lithium iron(II)phosphor-olivines prepared by a novel carbothermal re-duction method[J].Electrochem Solid-State Lett,2003,6:A53-A55.
[24]Park K S,Sun J T,Chung H T,et al.Synthesis ofLiFePO4by co-precipitation and microwave heating[J].Electrochem Commun,2003,5:839-842.
[25]TANG Chang-ping(唐昌平),YING Jie-rong(应皆荣),LEI Min(雷敏),et al.High density LiFePO4/Csynthesized by controlled crystallization and microwavecarbon thermal reduction[J].Electrochemistry(inChinese),2006,12(2):188-190.
[26]Ravet N,Gauthier M,Zaghib K,Goodenough J B,etal.Mechanism of the Fe3+reduction at low tempera-ture for LiFePO4synthesis from a polymeric additive[J].Chem Mater,2007,19:2595-2602.
[27]Chang H H,Chang C C,Wu H C,et al.Kineticstudy on low-temperature synthesis of LiFePO4via sol-id-state reaction[J].J Power Source,2006,158:550-556.
[28]Bamford C H,Tipper C F H.Comprehensive ChemicalKinetics,v.21,reactions of solids with gases[M].Amsterdam:Elsevier,1984.120.
[29]West A R.Solid state chemistry and its applications[M].New York:John Wiley and Sons,1984:439-440.
[30]Blazek A.Thermal analysis[M].London:Van Nos-trand Reinhold,1973.64.
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