A Synergistic Effect of Na+ and Al3+ Dual Doping on Electrochemical Performance and Structural Stability of LiNi0.88Co0.08Mn0.04O2 Cathodes for Li-Ion Batteries

The synergistic effect of Na⁺/Al³⁺ dual doping is investigated to improve the structural stability and electrochemical performance of LiNi_0.88Co_0.08Mn_0.04O₂ cathodes for Li-ion batteries. Rietveld refinement and density functional theory calculations confirm that Na⁺/Al³⁺ dual doping changes the lattice parameters of LiNi_0.88Co_0.08Mn_0.04O₂. The changes in the lattice parameters and degree of cation mixing can be alleviated by maintaining the thickness of the LiO₆ slab because the energy of Al-O bonds is higher than that of transition metal (TM)-O bonds. Moreover, Na is an abundant and inexpensive metal, and unlike Al³⁺, Na⁺ can be doped into the Li slab. The ionic radius of Na⁺ (1.02 Å) is larger than that of Li⁺ (0.76 Å); therefore, when Na⁺ is inserted into Li sites, the Li slab expands, indicating that Na⁺ serves as a pillar ion for the Li diffusion pathway. Upon dual doping of the Li and TM sites of Ni-rich Ni_0.88Co_0.08Mn_0.04O₂ (NCM) with Na⁺ and Al³⁺, respectively, the lattice structure of the obtained NNCMA is more ideal than those of bare NCM and Li⁺- and Na⁺-doped NCM (NNCM and NCMA, respectively). This suggests that NNCMA with an ideal lattice structure presents several advantages, namely, excellent structural stability, a low degree of cation mixing, and favorable Li-ion diffusion. Consequently, the rate capability of NNCMA (83.67%, 3 C/0.2 C), which presents favorable Li-ion diffusion because of the expanded Li sites, is higher than those of bare NCM (78.68%), NNCM (81.15%), and NCMA (83.18%). The Rietveld refinement, differential capacity analysis, and galvanostatic intermittent titration technique results indicate that NNCMA exhibits low polarization, favorable Li-ion diffusion, and a low degree of cation mixing; moreover, its phase transition is hindered. Consequently, NNCMA demonstrates a higher capacity retention (84%) than bare NCM (79%), NNCM (82%), and NCMA (82%) after 50 cycles at 1 C. This study provides insight into the fabrication of Ni-rich NCMs with excellent electrochemical performance.