M3-MODIFIED LIMN2O4 SPINEL INTERCALATION CATHODES .2. ELECTROCHEMICALSTABILIZATION BY CR3+()

The 4 V rechargeable capacity of the spinel LiMn2O4 was stabilized by substituting less than 1 mole percent (m/o) Mn3+ with Cr3+. The optimu m composition was determined as LiCr0.012Mn1.988O4, which had a discha rge capacity exceeding 110 mAh/g even after 100 cycles, although impro ved stabilities were attained for all Cr-modified compositions studied (0.1 to 7.0 m/o Cr3+ substitution): The effects of varying electrolyt e salt, temperature, and current density were also investigated. Capac ity losses in 4 V LiMn2O4-based spinel systems were attributed to Mn d issolution into the electrolyte causing structural degradation of the cathode and an increase in cell polarization from deposited Mn interfe ring with Li+ transport through the anodic solid-electrolyte interphas e. Substitution of even a small amount of Mn3+ by trivalent Cr3+ minim ized this dissolution and resulted in enhanced cathodic electrochemica l stability.