Abstract
Lithium substituted Li1+xMn2- xO4 spinel samples in the entire solid solution range (0≤x≤1/3) were synthesized by solid-state reaction. The samples with x<0.25 are stoichiometric and those with x≥0.25 are oxygen deficient. High-temperature oxide melt solution calorimetry in molten 3Na 2O·4MoO3 at 974 K was performed to determine their enthalpies of formation from constituent binary oxides at 298 K. The cubic lattice parameter was determined from least-squares fitting of powder XRD data. The variations of the enthalpy of formation from oxides and the lattice parameter with x follow similar trends. The enthalpy of formation from oxides becomes more exothermic with x for stoichiometric compounds (x<0.25) and deviates endothermically from this trend for oxygen-deficient samples (x≥0.25). This energetic trend is related to two competing substitution mechanisms of lithium for manganese (oxidation of Mn3+ to Mn 4+ versus formation of oxygen vacancies). For stoichiometric spinels, the oxidation of Mn3+ to Mn4+ is dominant, whereas for oxygen-deficient compounds both mechanisms are operative. The endothermic deviation is ascribed to the large endothermic enthalpy of reduction.
Original language | English (US) |
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Pages (from-to) | 1182-1189 |
Number of pages | 8 |
Journal | Journal of Solid State Chemistry |
Volume | 178 |
Issue number | 4 |
DOIs | |
State | Published - Apr 2005 |
Externally published | Yes |
Keywords
- Enthalpy of formation
- LiMnO
- Lithium ion batteries
- Spinel
- Thermodynamics
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Ceramics and Composites
- Condensed Matter Physics
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry