TY - JOUR
T1 - Enthalpy of formation of LiNiO2, LiCoO2 and their solid solution, LiNi1-xCoxO2
AU - Wang, Miaojun
AU - Navrotsky, Alexandra
N1 - Funding Information:
The authors thank Sarah Roeske and Greg Baxter for the electron probe microanalysis and Sergey Ushakov for helpful discussion on Rietveld refinement. This work was supported by the U.S. Department of Energy (grant DE-FG0397SF 14749).
PY - 2004/1/15
Y1 - 2004/1/15
N2 - LiCoO2, LiNiO2 and their solid solution, LiNi 1-xCoxO2, are important cathode materials for lithium ion batteries. Samples in this system were synthesized by solid state reaction of Co3O4, NiO and Li2CO3 or LiOH·H2O. Their lattice parameters were determined by Rietveld refinement. High temperature drop solution calorimetry in molten 3Na2O·4MoO3 and 2PbO·B2O 3 solvents at 974 K was performed to determine the enthalpy of formation from the constituent oxides plus oxygen and the enthalpy of mixing in the solid solution series. There are approximately linear correlations between the lattice parameters, the enthalpy of formation from oxides (Li2O, NiO and CoO) plus O2 and the Co content in the compounds. The solid solution of LiCoO2 and LiNiO2 is almost ideal, showing a small positive enthalpy of mixing. The enthalpy of formation of LiCoO 2 from oxides (Li2O, NiO and CoO) and oxygen at 298 K is -142.5±1.7 kJ/mol (from sodium molybdate calorimetry) or -140.2±2.3 kJ/mol (from lead borate calorimetry). That of LiNiO 2 is -56.2±1.5 kJ/mol (from sodium molybdate calorimetry) or -53.4±1.7 kJ/mol (from lead borate calorimetry). The cobalt compound is thus significantly more stable than its nickel analogue. The phase assemblage LiCoO2, Li2O and CoO is seen at a lower oxygen pressure at constant temperature than the assemblage Co3O4/CoO, reflecting the stabilization of Co(III) in the ternary Li-Co-O system.
AB - LiCoO2, LiNiO2 and their solid solution, LiNi 1-xCoxO2, are important cathode materials for lithium ion batteries. Samples in this system were synthesized by solid state reaction of Co3O4, NiO and Li2CO3 or LiOH·H2O. Their lattice parameters were determined by Rietveld refinement. High temperature drop solution calorimetry in molten 3Na2O·4MoO3 and 2PbO·B2O 3 solvents at 974 K was performed to determine the enthalpy of formation from the constituent oxides plus oxygen and the enthalpy of mixing in the solid solution series. There are approximately linear correlations between the lattice parameters, the enthalpy of formation from oxides (Li2O, NiO and CoO) plus O2 and the Co content in the compounds. The solid solution of LiCoO2 and LiNiO2 is almost ideal, showing a small positive enthalpy of mixing. The enthalpy of formation of LiCoO 2 from oxides (Li2O, NiO and CoO) and oxygen at 298 K is -142.5±1.7 kJ/mol (from sodium molybdate calorimetry) or -140.2±2.3 kJ/mol (from lead borate calorimetry). That of LiNiO 2 is -56.2±1.5 kJ/mol (from sodium molybdate calorimetry) or -53.4±1.7 kJ/mol (from lead borate calorimetry). The cobalt compound is thus significantly more stable than its nickel analogue. The phase assemblage LiCoO2, Li2O and CoO is seen at a lower oxygen pressure at constant temperature than the assemblage Co3O4/CoO, reflecting the stabilization of Co(III) in the ternary Li-Co-O system.
KW - Enthalpy of formation
KW - LiCoO
KW - LiNi CoO
KW - LiNiO
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U2 - 10.1016/j.ssi.2003.11.004
DO - 10.1016/j.ssi.2003.11.004
M3 - Article
AN - SCOPUS:1442311643
SN - 0167-2738
VL - 166
SP - 167
EP - 173
JO - Solid State Ionics
JF - Solid State Ionics
IS - 1-2
ER -