Solid-State Chemistry and Electrochemistry of LiCo[sub 1/3]Ni[sub 1/3]Mn[sub 1/3]O[sub 2] for Advanced Lithium-Ion Batteries

The first-principles calculation on the crystal and electronic structures of a lithium insertion material of has been carried out to search new positive-electrode materials for advanced lithium-ion batteries. having a superlattice based on an -type structure is suggested to be stable. According to the calculations, formal charges of Co, Ni, and Mn in Å, Å) are, respectively, estimated to be +3, +2, and +4. The solid-state redox reactions of are investigated under the assumption of a lithium insertion scheme, and the reactions are shown to be formally for in for and for Manganese ions do not participate for the redox reactions in an entire range. The illustrated maps on the change in electron density for the solid-state redox reactions indicate that the charge balance is due to the loss or gain of electrons on oxygen ions while the redox centers are transition metal ions of Ni or Co. Reversible potentials of against a lithium electrode are also calculated and the possibility of implementation is discussed with respect to the computational chemistry based on the first-principles calculation. © 2004 The Electrochemical Society. All rights reserved.