Promoting cycling and thermal stability of ultrahigh-nickel oxide cathodes with well-controlled microstructure and stiffness
Utilization of ultrahigh-nickel LiNi_xCo_yMn_1-x-yO_2 (NCM) (x > 0.97) in Li-ion batteries can distinctively boost energy density through enhanced discharge capacity. However, capacity and thermal stability deteriorate as Ni content approaches the limit. Here, we propose a facile strategy by introducing high-valence tungsten (W) into ultrahigh-nickel polycrystalline LiNi_0.98Co_0.01Mn_0.01O_2 (PCNCM98). W-doped PCNCM98 (W-PCNCM98) exhibits refined, compactly stacked primary particles, whereas PCNCM98 shows equiaxial, non-uniform larger particles. The refined microstructure enhances mechanical strength: average particle hardness of W-PCNCM98 is 104 MPa, 1.5 times higher than PCNCM98 (68 MPa). This improved mechanical property suppresses lattice volume changes and relieves microcrack formation from H2–H3 phase transition. Consequently, cycling performance in pouch-type full cells is significantly enhanced, with capacity retention of 73% after 2000 cycles at 1 C and 25 °C, 54% higher than PCNCM98. Enhanced structural stability and strong electron affinity of W6+ also improve thermal stability: exothermic peak for W-PCNCM98 is postponed to 203 °C with heat generation of 1287 J g−1, versus 190 °C and 1528 J g−1 for PCNCM98. This high-valent doping strategy stabilizes ultrahigh-nickel NCM cathodes, accelerating large-scale EV applications.