Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High-Performance Cathode

Abstract

A novel two-step surface modification method that includes atomic layer deposition (ALD) of TiO₂ followed by post-annealing treatment on spinel LiNi_0.5Mn_1.5O₄ (LNMO) cathode material is developed to optimize the performance. The performance improvement can be attributed to the formation of a TiMn₂O₄ (TMO)-like spinel phase resulting from the reaction of TiO₂ with the surface LNMO. The Ti incorporation into the tetrahedral sites helps to combat the impedance growth that stems from continuous irreversible structural transition. The TMO-like spinel phase also alleviates the electrolyte decomposition during electrochemical cycling. 25 ALD cycles of TiO₂ growth are found to be the optimized parameter toward capacity, Coulombic efficiency, stability, and rate capability enhancement. A detailed understanding of this surface modification mechanism has been demonstrated. This work provides a new insight into the atomic-scale surface structural modification using ALD and post-treatment, which is of great importance for the future design of cathode materials.

A novel method that combines atomic layer deposition of TiO₂ and post-annealing has been developed to fully exploit the performance of LiNi_0.5Mn_1.5O₄. The incorporation of Ti into both the tetrahedral and octahedral sites in the spinel structure suppresses the irreversible surface phase transition during initial charge and contributes to improved performance under both room temperature and 55 °C.

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