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Li₄Ti₅O₁₂ has excellent structural stability and high safety under fast charging and discharging conditions. Therefore, it was favored by the field of new energy vehicles and energy storage. Ample researchers have focused on Li ions intercalation process of lithium titanate, Studies have shown that the discharge process is the external and all the lithium ions located at 8a position are transferred to 16c position, and the capacity of lithium titanate is limited by the number of lattice sites and reversible lithium ions involved in it. However, the lithium titanate unit cell structure suggests that the lattice sites that accommoddate lithium ions do not stop there. Li ions may replace Ti atoms occupy the octahedral 16d site, locate in tetrahedral 48f sites, reoccupy with 8a sites of the tetrahedron vacated after the phase change. This article mainly reviews, treated by chemical or electrochemical methods in the preparation process and finished product, compared with the normal LTO discharge start and end, the Li ions occupation changes and influence. Meanwhile, this paper discusses and analyzes the underlying mechanism between this change and effect.