Citation: XIONG Li-Long, XU You-Long, TAO Tao. Synthesis and Electrochemical Characterization of Ge⁴⁺, Sn⁴⁺ Doped Spinel LiMn₂O₄[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201302211 shu

Synthesis and Electrochemical Characterization of Ge⁴⁺, Sn⁴⁺ Doped Spinel LiMn₂O₄

1.
Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education, Xi’an Jiaotong University, Xi’an 710049, P. R. China;International Center for Dielectric Research, Xi’an Jiaotong University, Xi’an 710049, P. R. China

Received Date: 3 December 2012
Available Online: 21 February 2013
Fund Project: 国家自然科学基金(21203145)资助项目 (21203145)

Spinel LiMn₂O₄ materials doped with tetravalent cations Ge⁴⁺ and Sn⁴⁺ were synthesized through solid-state reaction. Analysis of the materials by X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggested that Ge⁴⁺ ions occupied octahedral sites by substituting Mn⁴⁺ ions in the spinel structure to form the solid solution LiMn_2-xGe_xO₄ (x=0.02, 0.04, 0.06), while Sn⁴⁺ ions were present at the surface of the spinel LiMn₂O₄ as SnO₂. The substitution of Mn⁴⁺ with Ge⁴⁺ could suppress the long-range ordering of the Li⁺ ions in the spinel LiMn₂O₄, enhancing its stability. SnO₂ on the surface of LiMn₂O₄ could reduce the acidity of the liquid electrolyte, suppressing acid etching of the LiMn₂O₄ active material. Galvanostatic charge/ discharge tests showed that both Ge⁴⁺ and Sn⁴⁺-modified spinel LiMn₂O₄ materials exhibited significantly higher capacity retention than LiMn₂O₄. The increased capacity retention should benefit the application of spinel LiMn₂O₄ as a cathode material for lithium-ion batteries.
- Spinel LiMn₂O₄,
- Ge⁴⁺ doping,
- Sn⁴⁺ doping,
- Solid-state reaction,
- Cycleability
1. [1]
  
  (1) Zabula, A. V.; Filatov, A. S.; Spisak, S. N.; Rogachev, A. Y.;Petrukhina, M. A. Science 2011, 333, 1008. doi: 10.1126/science.1208686
2. [2]
  (2) Dunn, B.; Kamath, H.; Tarascon, J. M. Science 2011, 334, 928.doi: 10.1126/science.1212741
3. [3]
  (3) Magasinski, A.; Dixon, P.; Hertzberg, B.; Kvit, A.; Ayala, J.;Yushin, G. Nat. Mater. 2010, 9, 353. doi: 10.1038/nmat2725
4. [4]
  (4) Ryou, M. H.; Lee, Y. M.; Park, J. K.; Choi, J.W. Adv. Mater.2011, 23, 3066. doi: 10.1002/adma.201100303
5. [5]
  (5) Armstrong, A. R.; Kuganathan, N.; Islam, M. S.; Bruce, P. G.J. Am. Chem. Soc. 2011, 133, 13031. doi: 10.1021/ja2018543
6. [6]
  (6) Wang, J.; Li, T. J.; Qi, L. Acta Phys. -Chim. Sin. 2007, 23, 75.[王剑, 李桐进, 其鲁. 物理化学学报, 2007, 23, 75.]doi: 10.3866/PKU.WHXB2007Supp16
7. [7]
  (7) An, H. L.;Wu, N. N.; Lei, X. L.; Xu, J. L.; Qi, L. ActaPhys. -Chim. Sin. 2007, 23, 60. [安洪力, 吴宁宁, 雷向利,徐金龙, 其鲁, 物理化学学报, 2007, 23, 60.] doi: 10.3866/PKU.WHXB2007Supp14
8. [8]
  (8) Kang, B.; Ceder, G. Nature 2009, 458, 190. doi: 10.1038/nature07853
9. [9]
  (9) Wu, F.; Tan, G.; Chen, R.; Li, L.; Xiang, J.; Zheng, Y. Adv.Mater. 2011, 23, 5081. doi: 10.1002/adma.201103161
10. [10]
  (10) Yamamoto, K.; Iriyama, Y.; Asaka, T.; Hirayama, T.; Fujita, H.;Fisher, C. A. J.; Nonaka, K.; Sugita, Y.; Ogumi, Z. Angew.Chem. Int. Edit. 2010, 49, 4414. doi: 10.1002/anie.200907319
11. [11]
  (11) Ozawa, K. Solid State Ionics 1994, 69, 212. doi: 10.1016/0167-2738(94)90411-1
12. [12]
  (12) Amatucci, G. G.; Tarascon, J. M.; Klein, L. C. J. Electrochem.Soc. 1996, 143, 1114. doi: 10.1149/1.1836594
13. [13]
  (13) Bhattacharyya, R.; Key, B.; Chen, H.; Best, A. S.; Hollenkamp,A. F.; Grey, C. P. Nat. Mater. 2010, 9, 504. doi: 10.1038/nmat2764
14. [14]
  (14) Tarascon, J. M.;Wang, E.; Shokoohi, F. K.; McKinnon,W. R.;Colson, S. J. Electrochem. Soc. 1991, 138, 2859. doi: 10.1149/1.2085330
15. [15]
  (15) Lee, H.W.; Muralidharan, P.; Ruffo, R.; Mari, C. M.; Cui, Y.;Kim, D. K. Nano Lett. 2010, 10, 3852. doi: 10.1021/nl101047f
16. [16]
  (16) Arumugam, D.; Kalaignan, G. P.; Manisankar, P. Solid StateIonics 2008, 179, 580. doi: 10.1016/j.ssi.2008.04.010
17. [17]
  (17) Iqbal, A.; Iqbal, Y.; Chang, L.; Ahmed, S.; Tang, Z.; Gao, Y.J. Nanopart. Res. 2012, 14, 1206. doi: 10.1007/s11051-012-1206-9
18. [18]
  (18) Sigala, C.; Verbaere, A.; Mansot, J. L.; Guyomard, D.; Piffard,Y.; Tournoux, M. J. Solid State Chem. 1997, 132, 372. doi: 10.1006/jssc.1997.7476
19. [19]
  (19) Wang, G. X.; Bradhurst, D. H.; Liu, H. K.; Dou, S. X. SolidState Ionics 1999, 120, 95. doi: 10.1016/S0167-2738(98)00554-2
20. [20]
  (20) Myung, S. T.; Komaba, S.; Kumagai, N. J. Electrochem. Soc.2001, 148, A482.
21. [21]
  (21) Ryu,W. H.; Eom, J. Y.; Yin, R. Z.; Han, D.W.; Kim,W. K.;Kwon, H. S. J. Mater. Chem. 2011, 21, 15337. doi: 10.1039/c1jm10146c
22. [22]
  (22) Song, J.W.; Nguyen, C. C.; Choi, H.; Lee, K. H.; Han, K. H.;Kim, Y. J.; Choy, S.; Song, S.W. J. Electrochem. Soc. 2011,158, A458.
23. [23]
  (23) Xiong, L. L.; Xu, Y. L.; Zhang, C.; Tao, T. Acta Phys. -Chim.Sin. 2012, 28, 1177. [熊礼龙, 徐友龙, 张成, 陶韬,物理化学学报, 2012, 28, 1177.] doi: 10.3866/PKU.WHXB201203092
24. [24]
  (24) Xiong, L. L.; Xu, Y. L.; Tao, T.; odenough, J. B. J. PowerSources 2012, 199, 214. doi: 10.1016/j.jpowsour.2011.09.062
25. [25]
  (25) Arora, P.; Popov, B. N.; White, R. E. J. Electrochem. Soc. 1998,145, 807. doi: 10.1149/1.1838349
26. [26]
  (26) Mandal, S.; Rojas, R. M.; Amarilla, J. M.; Calle, P.; Kosova, N.V.; Anufrienko, V. F.; Rojo, J. M. Chem. Mater. 2002, 14, 1598.doi: 10.1021/cm011219v
27. [27]
  (27) Song, G. M.; Li,W. J.; Zhou, Y. Mater. Chem. Phys. 2004, 87,162. doi: 10.1016/j.matchemphys.2004.05.023
28. [28]
  (28) LeCras, F.; Bloch, D.; Anne, M.; Strobel, P. Solid State Ionics1996, 89, 203. doi: 10.1016/0167-2738(96)00345-1
29. [29]
  (29) Cho, Y.; Lee, S.; Lee, Y.; Hong, T.; Cho, J. Adv. Energy Mater.2011, 1, 821. doi: 10.1002/aenm.201100239
30. [30]
  (30) Wu, H. M.; Tu, J. P.; Chen, X. T.; Li, Y.; Zhao, X. B.; Cao, G. S.J. Solid State Electrochem. 2007, 11, 173.
31. [31]
  (31) Li, G. H.; Ikuta, H.; Uchida, T.;Wakihara, M. J. Electrochem.Soc. 1996, 143, 178. doi: 10.1149/1.1836405
32. [32]
  (32) Arumugam, D.; Kalaignan, G. P.; Vediappan, K.; Lee, C.W.Electrochim. Acta 2010, 55, 8439. doi: 10.1016/j.electacta.2010.07.033
33. [33]
  (33) Ein-Eli, Y.;Wen,W.; Mukerjee, S. Electrochem. Solid State Lett.2005, 8, A141.
34. [34]
  (34) Xiong, L. L.; Xu, Y. L.; Zhang, C.; Zhang, Z.W.; Li, J. B.J. Solid State Electrochem. 2011, 15, 1263. doi: 10.1007/s10008-010-1195-5
35. [35]
  (35) Xiong, L. L.; Xu, Y. L.; Tao, T.; Du, X. F.; Li, J. B. J. Mater.Chem. 2011, 21, 4937. doi: 10.1039/c0jm03498c
36. [36]
  (36) Krins, N.; Hatert, F.; Traina, K.; Dusoulier, L.; Molenberg, I.;Fagnard, J. F.; Vanderbemden, P.; Rulmont, A.; Cloots, R.;Vertruyen, B. Solid State Ionics 2006, 177, 1033. doi: 10.1016/j.ssi.2006.04.001
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沈阳化工大学材料科学与工程学院沈阳 110142

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Synthesis and Electrochemical Characterization of Ge⁴⁺, Sn⁴⁺ Doped Spinel LiMn₂O₄