Synthesis, Characterization and Electrochemical Performance of Nb Doped LiFePO4/C Cathodes by Mechanochemical Activation

Abstract

We synthesized Nb-doped LiFePO4/C nano composite cathode materials by mechanochemical activation followed by a single step calcination. The starting chemicals of Li2CO3, FeC2O4.2H2O, NH4H2.PO4 and C6H8O7 as lithium, iron, phosphate, and carbon sources are mixed in a high energy ball mill (250 rpm, 5h) and calcined at 650 °C and 10 hours. The resultant materials are structurally (XRD, SEM, TEM) and electrochemically characterized and high purity LiFePO4 with high electrochemical performance is obtained. Voltage vs. specific capacity, discharge capacity vs. cycle number in manufactured battery is presented. An initial specific discharge capacity of 153 mAhg−1 and a specific discharge capacity of 128.4 mAhg−1 after the 8th charge/discharge cycling at 1C is recorded.

Keywords:

LiFePO4, Lithium ion battery, Mechanochemical activation, Nb doping

DOI: 10.17350/HJSE19030000077

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Research Article

References

1. Xie G, Zhu H-J, Liu X-M, and Yang H. A core–shell LiFePO4/C nanocomposite prepared via a sol–gel method assisted by citric acid. Journal of Alloys and Compounds 574 (2013) 155–160.

2. Johnson ID, Blagovidova E, Dingwall PA, Brett DJL, Shearing PR. Darr JA. High power Nb-doped LiFePO4 Li-ion battery cathodes; pilot-scale synthesis and electrochemical properties. Journal of Power Sources 326 (2016) 476e481

3. Toprakci O, Toprakci HAK, Ji L, Zhang X. Fabrication and electrochemical characteristics of LiFePO4 powders for lithium-ion batteries. Kona Powder and Particle Journal 28 (2010) 50-72.

4. Franger S, Cras FL, Bourbon C, Rouault H. Comparison between different LiFePO4 synthesis routes and their influence on its physico-chemical properties. Journal of Power Sources 119–121 (1) (2003) 252–257.

5. Franger S, Benoit C, Bourbon C, Cras FL. Chemistry and electrochemistry of composite LiFePO4 materials for secondary lithium batteries. Journal of Physics and Chemistry of Solids. 67 (5-6) (2006) 1338–1342.

6. Park CK, Hwang JT, Cho WI and Jang H. The origin of the residual carbon in LiFePO4 synthesized by wet milling. Bull Korean Chem Soc. 32 (2) (2011) 536-540.

7. Shin HC, Park SB, Jang H, Chung KY, Cho WI, Kim CS, Cho BW. rate performance and structural change of cr-doped LiFePO4/C during cycling. Electrochemica Acta 53 (2008) 7946–7951.

8. Li C, Hua N, Wang C, Kang X. Effect of Mn2+ doping in LiFePO4 and the low temperature electrochemical performances. Journal of Alloys and Compounds 509 (2011) 1897–1900.

9. Park CK, Park SB, Park CH, Shin HC, Cho WI and Jang H. The root cause of the rate performance improvement after metal doping: a case study of LiFePO4. Bull Korean Chem Soc. 32 (3) (2011) 921-926.

10. Ma Z, Shao G, Wang G, Zhang Y and Du J. Effects of Nb-doped on the structure and electrochemical performance of LiFePO4/C composites. Journal of Solid State Chemistry 210 (1) (2014) 232–237.

11. Zhang, Q, Wang S, Zhou Z, Ma G, Jiang W, Guo X, Zhao S. Structural and electrochemical properties of Nd-doped LiFePO4/C prepared without using inert gas. Solid State Ionics 191 (2011) 40–44.

12. Zhuang D, Zhao X, Xie J, Tu J, Zhu T, Cao G. One-step Solid-state Synthesis and Electrochemical Performance of Nb-doped LiFePO4/C. ActaPhys.Chim.Sin. 22 (2006) 840–844.

13. Morales J, Trócoli R, Rodríguez-Castellón E, Franger S, Santos-Peña J. Effect of C and Au additives produced by simple coaters on the surface and the electrochemical properties of nanosized LiFePO4. Journal of Electroanalytical Chemistry 63 (2009) 29–35.

14. Suo L, Han W, Lu X, Gu L, Hu YS, Li H, Chen D, Chen L, Tsukimoto S and Ikuhara Y. Highly ordered staging structural interface between LiFePO4 and FePO4. Phys Chem Chem. Phys. 14 (2012) 5363-5367.

15. Zhang D, Yu X, Wang Y, Cai R, Shao Z, Liao X-Z, and MaZ-F. Ball milling-assisted synthesis and electrochemical performance of LiFePO4/C for lithium-ion battery adopting citric acid as carbon precursor. Journal of the Electrochemical Society 156 (10) (2009) A802- A808.

16. Li M, Xie K, Li D, and Pan Y. Synthesis of LiFePO4 by one-step annealing under the vacuum condition. Journal of Materials Science 40 (2005) 2639–2641.

17. Kim J-K, Choi J-W, Chauhan GS, Ahn J-H, Hwang G-C, Choi J-B and Ahn H-J. Enhancement of electrochemical performance of lithium iron phosphate by controlled sol–gel synthesis. Electrochimica Acta 53 (28) (2008) 8258–8264.

18. Koltypin M, Aurbach D, Nazar L and Ellis B. More on the performance of LiFePO4 electrodes—the effect of synthesis route, solution composition, aging, and temperature. Journal of Power Sources 174 (2) (2007) 1241–1250.

19. Kosova N, Devyatkina E. On mechanochemical preparation of materials with enhanced characteristics for lithium batteries. Solid State Ionics 172 (1-4) (2004) 181–184.

20. Lee J, Kumar P, Lee G, Moudgil BM and Singh RK. Electrochemical performance of surfactant-processed LiFePO4 as a cathode material for lithium-ion rechargeable batteries. Ionics, 19(2) (2012) 371–378.

21. Ojczyk W, Marzec J, Świerczek K, Zając W, Molenda M, Dziembaj R and Molenda J. Studies of selected synthesis procedures of the conducting LiFePO4-based composite cathode materials for li-ion batteries. Journal of Power Sources 173(2) (2007) 700–706.

22. Fey GTK, Chen YG and Kao HM. Electrochemical properties of LiFePO4 prepared via ball-milling. Journal of Power Sources 189 (1) (2009) 169–178.

23. Fey GTK and Lu TL. Morphological characterization of LiFePO4/C composite cathode materials synthesized via a carboxylic acid route. Journal of Power Sources 178 (2)(2008) 807–814.

24. Yun NJ, Ha HW, Jeong KH, Park HY and Kim K. Synthesis and electrochemical properties of olivine-type LiFePO4/C composite cathode material prepared from a poly(vinyl alcohol)-containing precursor. Journal of Power Sources 160 (2) (2006) 1361–1368.

25. Wang D, Li H, Wang Z, Wu X, Sun Y, Huang X and Chen L. New solid state synthesis routine and mechanism for LiFePO4 using LiF as lithium precursor. Journal of Solid State Chemistry, 177(12) (2004) 4582–4587.

26. Lv YJ, Su J, Long YF, Cui XR, Lv XY and Wen YX. Effects of ball-to-powder weight ratio on the performance of LiFePO4/C prepared by wet-milling assisted carbothermal reduction. Powder Technology 253 (2014) 467–473.

27. Chen Z, Ren Y, Qin Y, Wu H, Ma S, Ren J, He X, Sun YK, Amine K. Solid state synthesis of LiFePO4 studied by in situ high energy x-ray diffraction. Journal of Materials Chemistry 21(15) (2011) 5604–5609.

28. Kayyar A, Huang J, Samiee M, Luo J. Construction and testing of coin cells of lithium ion batteries. J Vis Exp 66 (e4104) (2012) 1–5.

29. Kim HS, Kam DV, Kim VS, Koo HJ. Synthesis of the LiFePO4 by a solid-state reaction using organic acids as a reducing agent. Ionics 17 (4) (2011) 293–297.
Published
2018-03-28
Section
ENGINEERING