Thermodynamic Stability of Transition-Metal-Substituted LiMn2−xMxO4 (M=Cr, Fe, Co, and Ni) Spinels

Chenying Lai, Jiewei Chen, James C. Knight, Arumugam Manthiram, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


The formation enthalpies from binary oxides of LiMn2O4, LiMn2−xCrxO4 (x=0.25, 0.5, 0.75 and 1), LiMn2−xFexO4 (x=0.25 and 0.5), LiMn2−xCoxO4 (x=0.25, 0.5, and 0.75) and LiMn1.75Ni0.25O4 at 25 °C were measured by high temperature oxide melt solution calorimetry and were found to be strongly exothermic. Increasing the Cr, Co, and Ni content leads to more thermodynamically stable spinels, but increasing the Fe content does not significantly affect the stability. The formation enthalpies from oxides of the fully substituted spinels, LiMnMO4 (M=Cr, Fe and Co), become more exothermic (implying increasing stability) with decreasing ionic radius of the metal and lattice parameters of the spinel. The trend in enthalpy versus metal content is roughly linear, suggesting a close-to-zero heat of mixing in LiMn2O4—LiMnMO4 solid solutions. These data confirm that transition-metal doping is beneficial for stabilizing these potential cathode materials for lithium-ion batteries.

Original languageEnglish (US)
Pages (from-to)1973-1978
Number of pages6
StatePublished - Jul 4 2016
Externally publishedYes


  • calorimetry
  • doping effect
  • lithium-ion batteries
  • spinel phases
  • thermodynamics

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry


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