Journal of Central South University

, Volume 18, Issue 2, pp 314–318 | Cite as

Structure and stability of Li-Mn-Ni composite oxides as lithium ion sieve precursors in acidic medium

  • Li-wen Ma (马立文)
  • Bai-zhen Chen (陈白珍)
  • Xi-chang Shi (石西昌)Email author
  • Wen Zhang (张文)
  • Xi-yun Yang (杨喜云)


A series of spinel Li-Mn-Ni composite oxides with theoretical chemical formula of LiNixMn2−xO4 (0≤x≤1.0) were synthesized by liquid phase method. Their structure and morphology were characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM), respectively. The stability of these Ni-substituted spinel oxides prepared at different temperatures was investigated in acidic medium as well. The results show that Ni can be brought into the spinel framework completely to form well-crystallized product when x≤0.5 and the optimized synthesis temperature is 800 °C. LiNi0.4Mn1.6O4 prepared at 800 °C can maintain the spinel structure and morphology with Li extraction ratio of 30.37%, Mn extraction ratio of 8.78% and Ni extraction ratio of 1.82% during acid treatment. The incorporated Ni not only inhibits the dissolution of Mn, but also reduces the extraction of Li due to the lattice contraction.

Key words

lithium ion sieve Li-Mn-Ni composite oxide structure stability 


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  1. [1]
    CHEN Ting, YAN Shu-yi, KANG Zi-hua. Progress on the extraction of lithium from the salt lake brine in China [J]. Salt and Chemical Industry, 2006, 36(2): 19–21. (in Chinese)Google Scholar
  2. [2]
    CHEN Bai-zhen, MA Li-wen, SHI Xi-chang, XU Hui, YANG Xi-yun. Research progress on preparation methods for precursors of lithium ion sieve [J]. Inorganic Chemicals Industry, 2009, 41(7): 1–4. (in Chinese)Google Scholar
  3. [3]
    HUNTER J C. Preparation of a new crystal form of manganese dioxide: λ-MnO2 [J]. Journal of Solid State Chemistry, 1981, 39: 142–147.CrossRefGoogle Scholar
  4. [4]
    OOI K, MIYAI Y, SAKAKIHARA, Mechanism of Li+ insertion in spinel-type manganese oxide: Redox and ion-exchange reactions [J]. Langmuir, 1991, 7: 1167–1171.CrossRefGoogle Scholar
  5. [5]
    FENG Q, MIYAI Y, KANOH H, OOI K. Li+ extraction/insertion with spinel-type lithium manganese oxides: Characterization of redox-type and ion-exchange-type sites [J]. Langmuir, 1992, 8: 1861–1867.CrossRefGoogle Scholar
  6. [6]
    FENG Q, MIYAI Y, KANOH H, OOI K. Li+ and Mg2+ extraction and Li+ insertion reactions with LiMg0.5Mn1.5O4 spinel in the aqueous phase [J]. Chem Mater, 1993, 5: 311–316.CrossRefGoogle Scholar
  7. [7]
    LIU Yi-fan, FENG Qi, OOI K. The synthesis and ion-exchange property of Li+ memorized spinel LiAlMnO4 [J]. Ion Exchange and Adsorption, 1995, 11(3): 216–222.Google Scholar
  8. [8]
    DONG Dian-quan, ZHONG Jie, LIU Dun-lei, LIU Yi-fan. Synthesis of LiCu0.5Mn1.5O4 and its Li+ extraction/insertion reaction in aqueous solution [J]. Chinese Journal of Applied Chemistry, 1998(3): 114–115. (in Chinese)Google Scholar
  9. [9]
    DONG Dian-quan, ZHANG Feng-bao, ZHANG Guo-lian, LIU Yi-fan. LiMg0.5Mn1.5O4 synthesis and its selectivity to Li+ exchange [J]. Chinese Journal of Inorg Chem, 2004, 20(9): 1126–1130. (in Chinese)Google Scholar
  10. [10]
    LIU Y F, FENG Q, OOI K. Li+ extraction/insertion reactions with LiAlMnO4 and LiFeMnO4 spinels in the aqueous phase [J]. J Colloid Interface Sci, 1994, 163(1): 130–136.CrossRefGoogle Scholar
  11. [11]
    CHITRAKAR R, KANOH H, MAKITA Y, MIYAI Y, OOI K. Synthesis of spinel-type lithium antimony manganese oxides and their Li+ extraction/insertion reactions [J]. J Mater Chem, 2000, 10: 2325–2329.CrossRefGoogle Scholar
  12. [12]
    TIAN Li-yan, MA Wei, HAN Mei. Adsorption behavior of Li+ onto nano-lithium ion sieve from hybrid magnesium/lithium manganese oxide [J]. Chemical Engineering Journal, 2010, 156: 134–140.CrossRefGoogle Scholar
  13. [13]
    GUO Hua-jun, LI Xin-hai, ZHANG Xin-ming, ZENG Su-ming, WANG Zhi-xin, PENG Wen-jie. Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries [J]. J Cent South Univ Technol, 2005, 12(s1): 44–49.CrossRefGoogle Scholar
  14. [14]
    WANG Zhi-xing, FANG Hai-sheng, YIN Zhou-lan, LI Xin-hai, GUO Hua-jun, PENG Wen-jie. Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction [J]. J Cent South Univ Technol, 2005, 12(s1): 54–58.CrossRefGoogle Scholar
  15. [15]
    YANG S H, RICHARD L M. Redox reactions of cobalt, aluminum and titanium substituted lithium manganese spinel compounds in lithium cells [J]. Solid State Ionics, 2001, 139: 13–25.CrossRefGoogle Scholar
  16. [16]
    RAJA M W, MAHANTY S, BASU R N. Influence of S and Ni co-doping on structure, band gap and electrochemical properties of lithium manganese oxide synthesized by soft chemical method [J]. Journal of Power Sources, 2009, 192: 618–626.CrossRefGoogle Scholar
  17. [17]
    LIAO Li-bin, LI Guo-wu. X-ray diffraction methods and their application [M]. Beijing: Geology Press, 2008: 113–114. (in Chinese)Google Scholar

Copyright information

© Central South University Press and Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  • Li-wen Ma (马立文)
    • 1
  • Bai-zhen Chen (陈白珍)
    • 1
  • Xi-chang Shi (石西昌)
    • 1
    Email author
  • Wen Zhang (张文)
    • 1
  • Xi-yun Yang (杨喜云)
    • 1
  1. 1.School of Metallurgical Science and EngineeringCentral South UniversityChangshaChina

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