Surface modifications of Li-ion battery electrodes with various ultrathin amphoteric oxide coatings for enhanced cycleability

Ultrathin ZnO, ZrO₂, and Al₂O₃ surface coatings are deposited via atomic layer deposition (ALD) with high conformality and atomic scale thickness control to enhance the electrochemical performance of LiMn₂O₄ for applications in lithium ion batteries. Two types of ALD-modified LiMn₂O₄ electrodes are fabricated: one is ALD-coated LiMn₂O₄ composite electrode and the other is electrode composed of ALD-coated LiMn₂O₄ particles and uncoated carbon/polyvinylidenefluoride network. Cycling performance and cyclic voltammetric patterns reveal that ZnO ALD coating is the most effective protective film for improving the electrochemical performance of LiMn₂O₄ at either 25 or 55 °C, followed by ZrO₂ and Al₂O₃. After 100 electrochemical cycles in 1 C at 55 °C, the electrode consisting of LiMn₂O₄ particles coated with six ZnO ALD layers (as thin as ~1 nm) delivers the highest final capacity, more than twice that of the bare electrode. It is also found that amphoteric oxide coating on LiMn₂O₄ particles can enhance the cycleability of LiMn₂O₄ more effectively than coating on the composite electrode. Furthermore, for ALD coating either on the composite electrode or on LiMn₂O₄ particles, the effect of oxide ALD modification for improving capacity retention and increasing specific capacity of LiMn₂O₄ is more phenomenal at elevated temperature than at room temperature.