Please wait a minute...
Acta Phys. Chim. Sin.  2013, Vol. 29 Issue (07): 1507-1514    DOI: 10.3866/PKU.WHXB201304231
ELECTROCHEMISTRY AND NEW ENERGY     
Synthesis and Electrochemical Properties of LiFe1-xNbxPO4/C Composite Cathode Material by Two-Step Synthesis Route
CAO Yan-Bing1,2, LUO Liang1, DU Ke1, PENG Zhong-Dong1, HU Guo-Rong1, JIANG Feng2
1 School of Metallurgical Science and Engineering, Central South University, Changsha 410083;
2 School of Materials Science and Engineering, Central South University, Changsha 410083
Download:   PDF(1170KB) Export: BibTeX | EndNote (RIS)      

Abstract  

LiFePO4/C composite was prepared by two-step synthesis route, with LiH2PO4 and FeC2O4· 2H2O as starting materials. In the process, the carbon sources polyvinyl alcohol (PVA) and glucose were added in a stepwise fashion. The well-crystallized LiFePO4/C composite with homogeneous small particles was obtained after reacting at 700℃ for 4 h. This composite had a discharge specific capacity of 157.3 mAh·g-1 at 0.1C rate and 138.4 mAh·g-1 at 1C rate. On the basis of carbon coating modification, Nb-ion-doped LiFe1-xNbxPO4/C (x=0.005, 0.01, 0.015, 0.02) composites were prepared. The optimized LiFe0.99Nb0.01PO4/C cathode displayed a discharge specific capacity 160.5 mAh·g-1 at 0.1C discharge rate, 136.0 mAh·g-1 at 5C and maintained 134.8 mAh·g-1 after 50 cycles, showing good rate properties and cycling stability. Cyclic voltammetry (CV) measurements indicated that aliovalent dopant substituting on the Fe sites can reduce the resistance of Li ion diffusion in the electrode process, increase phase transformation kinetics during cycling, and enhance the reversibility of LiFePO4 electrodes.



Key wordsPolyanion cathode material      LiFePO4      Two-step synthesis      Nb doping     
Received: 18 January 2013      Published: 23 April 2013
MSC2000:  O646  
  TM912  
Fund:  

The project was supported by the National Key Technology R&D Program of China (2007BAE12B01), Fundamental Research Funds for the Central Universities, China (2012QNZT018), China Postdoctoral Science Foundation (2012M521546), and Postdoctoral Science Foundation of Central South University, China.

Corresponding Authors: PENG Zhong-Dong     E-mail: cybcsu@csu.edu.cn
Cite this article:

CAO Yan-Bing, LUO Liang, DU Ke, PENG Zhong-Dong, HU Guo-Rong, JIANG Feng. Synthesis and Electrochemical Properties of LiFe1-xNbxPO4/C Composite Cathode Material by Two-Step Synthesis Route. Acta Phys. Chim. Sin., 2013, 29(07): 1507-1514.

URL:

http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB201304231     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2013/V29/I07/1507

(1) Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B.J. Eletrochem. Soc. 1997, 144, 1188. doi: 10.1149/1.1837571
(2) Padhi, A. K.; Nanjundaswamy, K. S.; Masquelier, C.; Okada, S.;Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1609.
(3) Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587. doi: 10.1021/cm901452z
(4) Yamada, A.; Chung, S. C.; Hinokuma, K. J. J. Electrochem. Soc.2001, 148, A224.
(5) Morgan, D.; Van der Ven, A.; Ceder, G. Electrochem. Solid- State Lett. 2004, 7, A30.
(6) Fisher, C. A. J.; Hart Prieto, V. M.; Islam, M. S. Chem. Mater.2008, 20, 5907.
(7) Delacourt, C.; Poizot, P.; Levasseur, S.; Masquelier, C.Electrochem. Solid-State Lett. 2006, 9, A352.
(8) Lim, S. Y.; Yoon, C. S.; Cho, J. P. Chem. Mater. 2008, 20, 4560.doi: 10.1021/cm8006364
(9) Wang, Y. G.;Wang, Y. R.; Hosono, E.;Wang, K. X.; Zhou, H. S.Angew. Chem. Int. Edit. 2008, 47, 7461. doi: 10.1002/anie.v47:39
(10) Kang, B.; Ceder, G. Nature 2009, 458, 190.
(11) Chung, S. Y.; Bloking, J. T.; Chiang, Y. M. Nat. Mater. 2002, 1,123.
(12) Chen, Y.;Wang, Z. L.; Yu, C. Y.; Xia, D. G.;Wu, Z. Y. Acta Phys. -Chim. Sin. 2008, 24, 1498. [陈宇, 王忠丽, 于春洋,夏定国, 吴自玉. 物理化学学报, 2008, 24, 1498.] doi: 10.3866/PKU.WHXB20080829
(13) Zhang,W. J. J. Electrochem. Soc. 2010, 157, A1040.
(14) Dominko, R.; Gaberš?ek, M.; Drofenik, J.; Bele, M.; Pejovnik,S.; Jamnik, J. J. Power Sources 2003, 119 -121, 770.
(15) Yu, H. M.; Zheng,W.; Cao, G. S.; Zhao, X. B. Acta Phys. -Chim. Sin. 2009, 25, 2186. [余红明, 郑威, 曹高劭,赵新兵. 物理化学学报, 2009, 25, 2186.] doi: 10.3866/PKU.WHXB20091113
(16) Wang, Z. P.; Liu,W.;Wang, Y.; Zhao, C. S.; Zhang, S. P.; Chen,J.T.; Zhou, H. H.; Zhang, X. X. Acta Phys. -Chim. Sin. 2012, 28,2084. [王震坡, 刘文, 王悦, 赵春松, 张淑萍, 陈继涛, 周恒辉, 张新祥. 物理化学学报, 2012, 28, 2084.] doi: 10.3866/PKU.WHXB201207043
(17) Wang, D. Y.; Li, H.; Shi, S. Q.; Huang, X. J.; Chen, L. Q.Electrochim. Acta 2005, 50, 2955. doi: 10.1016/j.electacta.2004.11.045
(18) Wang, G. X.; Bewlay, S.; Needham, S.; Liu, H. K.; Liu, R. S.;Drozd, V. A.; Lee, J. F.; Chen, J. M. J. Electrochem. Soc. 2006,153, A25
(19) Maier, J.; Amin, R. J. Electrochem. Soc. 2008, 155, A339.
(20) Ning, L. J.;Wu, Y. P.; Fang, S. B.; Rahm, E.; Holze, R. J. Power Sources 2004, 133, 229. doi: 10.1016/j.jpowsour.2004.01.048
(21) Ong, C.W.; Lin, Y. K.; Chen, J. S. J. Electrochem. Soc. 2007,154, A527
(22) Zhang, P. X.;Wang, Y. Y.; Lin, M. C.; Zhang, D. Y.; Ren, X. Z.;Yuan, Q. H. J. Electrochem. Soc. 2012, 159, A402.
(23) Wang, J. J.; Sun, X. L. Energy Environ. Sci. 2012, 5, 5163. doi: 10.1039/c1ee01263k
(24) Nonglak, M.; Yu, H. K.; Scott, A. S.; Chiang, Y. M. Adv. Funct. Mater. 2009, 19, 1060. doi: 10.1002/adfm.v19:7
(25) Sun, C. S.; Zhou, Z.; Xu, Z. G.;Wang, D. G.;Wei, J. P.; Bian,X. K.; Yan, J. J. Power Sources 2009, 193, 841. doi: 10.1016/j.jpowsour.2009.03.061
(26) Yang, M. R.; Ke,W. H. J. Electrochem. Soc. 2008, 155, A729.
(27) Ma, J.; Li, B. H.; Du, H. D.; Xu, C. J.; Kang, F. Y.J. Electrochem. Soc. 2011, 158, A26.

[1] HE Lei, XU Jun-Min, WANG Yong-Jian, ZHANG Chang-Jin. LiFePO4-Coated Li1.2Mn0.54Ni0.13Co0.13O2 as Cathode Materials with High Coulombic Efficiency and Improved Cyclability for Li-Ion Batteries[J]. Acta Phys. Chim. Sin., 2017, 33(8): 1605-1613.
[2] ZHANG Ying-Jie, ZHU Zi-Yi, DONG Peng, QIU Zhen-Ping, LIANG Hui-Xin, LI Xue. New Research Progress of the Electrochemical Reaction Mechanism, Preparation and Modification for LiFePO4[J]. Acta Phys. Chim. Sin., 2017, 33(6): 1085-1107.
[3] REN Jian-Xin, HU You-Kun, GUO Xiao-Dong, TANG Yan, ZHONG Ben-He, LIU Heng. Vacuum-Assisted Synthesis of Fe3(PO4)2·8H2O and Its Influence on Structure, Morphology and Electrochemical Performance of LiFePO4/C[J]. Acta Phys. Chim. Sin., 2014, 30(5): 866-872.
[4] HU You-Kun, REN Jian-Xin, WEI Qiao-Ling, GUO Xiao-Dong, TANG Yan, ZHONG Ben-He, LIU Heng. Synthesis of Rod-Like LiFePO4/C Materials with Different Aspect Ratios by Polyol Process[J]. Acta Phys. Chim. Sin., 2014, 30(1): 75-82.
[5] SUN Chao, YAN Liu-Ming, YUE Bao-Hua. Improvement of Surface Structure and Enhancement of Conductivity of LiFePO4 Surface by Graphene and Graphene-Like B-C-N Coating[J]. Acta Phys. Chim. Sin., 2013, 29(08): 1666-1672.
[6] CAO Yan-Bing, DUAN Jian-Guo, JIANG Feng, HU Guo-Rong, PENG Zhong-Dong, DU Ke. Synthesis of LiFePO4 Cathode Materials by Mechanical-Activation-Assisted Polyol Processing[J]. Acta Phys. Chim. Sin., 2012, 28(05): 1183-1188.
[7] ZHAO Hao-Chuan, SONG Yang, GUO Xiao-Dong, ZHONG Ben-He, DONG Jing, LIU Heng. Effect of Precursor Ingredient Temperature on the Performance of LiFePO4 by Hydrothermal Method[J]. Acta Phys. Chim. Sin., 2011, 27(10): 2347-2352.
[8] CHU Dao-Bao, LI Yan, SONG Qi, ZHOU Ying. Synthesis and Properties of LiFePO4/C Cathode Material with a New Carbon Source[J]. Acta Phys. Chim. Sin., 2011, 27(08): 1863-1867.
[9] SU Chang, LU Guo-Qiang, XU Li-Huan, ZHANG Cheng, MA Chun-An. Synthesis and Properties of Spindle-Shaped LiFePO4 for the Cathode Material of Lithium Ion Battery[J]. Acta Phys. Chim. Sin., 2011, 27(03): 609-614.
[10] FU Mao-Hua, HUANG Ke-Long, LIU Su-Qin, LIU Jian-Sheng, LI Yong-Kun. Effect of Lithium Difluoro(oxalato)borate on the High-Temperature Performance of LiFePO4/Graphite Batteries[J]. Acta Phys. Chim. Sin., 2009, 25(10): 1985-1990.
[11] JIN Zheng-Wei; LIU Chang-Ling; LIANG Hao. Effects of pH on the Structure of Non-Ionically Templated MSU-X Mesoporous Silica via a Two-Step Synthesis[J]. Acta Phys. Chim. Sin., 2009, 25(01): 150-154.
[12] ZHUANG Da-Gao;ZHAO Xin-Bing;XIE Jian;TU Jian;ZHU Tie-Jun;CAO Gao-Shao. One-step Solid-state Synthesis and Electrochemical Performance of Nb-doped LiFePO4/C[J]. Acta Phys. Chim. Sin., 2006, 22(07): 840-844.
[13] XUE Ming-zhe; FU Zheng-wen. Electrochemical Properties of LiFePO4 Cathode Thin Film Fabricated by Pulsed Laser Deposition[J]. Acta Phys. Chim. Sin., 2005, 21(07): 707-710.
[14] LU Jun-Biao; TANG Zi-Long; ZHANG Zhong-Tai; JIN Yong-Zhu. Influence of Mg Ion Doping on the Battery Properties of LiFePO4/C[J]. Acta Phys. Chim. Sin., 2005, 21(03): 319-323.