Table 1. Calculated Formation Energies E_f of Intrinsic Defects in LiMn₂O₄ under Some O-Rich Equilibrium Conditions^a.

	Ef (eV)
defects	a	b	c	d	e
VLi	1.22	0.46	0.38	–0.09	–0.22
VMnIII	0.22	0.60	0.64	0.88	0.94
VMnIV	–0.13	0.25	0.29	0.53	0.59
VOIII	2.28	2.28	2.28	2.28	2.28
VOIV	2.30	2.30	2.30	2.30	2.30
LiMnIII	–1.43	–0.29	–0.17	0.54	0.73
LiMnIV	–1.22	–0.08	0.04	0.75	0.94
MnLi	2.84	1.70	1.58	0.87	0.68
ILiIII	1.28	2.04	2.12	2.59	2.72
ILiIV	1.00	1.76	1.84	2.31	2.44
IMnIII	4.14	3.76	3.72	3.48	3.42
IMnIV	3.98	3.60	3.56	3.32	3.26

^aa, b, c, d, and e represent the LiMnO₂, Li₂MnO₃, MnO₂, Mn₂O₃, Mn₃O₄ phases that coexist with O₂ and LiMn₂O₄, respectively. The negative values of formation energies indicate that LiMn₂O₄ would spontaneously form defects, and therefore, the assumption of local equilibrium under those conditions indicates instability.