Influence of Interlayer Cation Ordering on Na Transport in P2-Type Na0.67–xLiy Ni0.33–zMn0.67+zO2 for Sodium-Ion Batteries

• DOI: 10.1021/jacs.4c00869
• Publication Date: 2024-05-02T13:40:50Z
• Authors: Eric Gabriel; Zishen Wang; Vibhu Vardhan Singh; Kincaid Graff; Jue Liu; Cyrus Koroni; Dewen Hou; Darin Schwartz; Cheng Li; Juejing Liu; Xiaofeng Guo; Naresh C. Osti; Shyue Ping Ong; Hui Xiong

P2-type Na2/3Ni1/3Mn2/3O2 (PNNMO) has been extensively studied because of its desirable electrochemical properties as a positive electrode for sodium-ion batteries. PNNMO exhibits intralayer transition-metal ordering Ni and Mn Na+/vacancy ordering. The is often considered major impediment to fast Na+ transport can be affected by We show neutron/X-ray diffraction density functional theory (DFT) calculations that Li doping (Na2/3Li0.05Ni1/3Mn2/3O2, LFN5) promotes ABC-type interplanar Ni/Mn without disrupting the creates low-energy Li–Mn-coordinated diffusion pathways. A structure model developed quantitatively identify both cation mixing interlayer cationic stacking fault densities. Quasielastic neutron scattering reveals diffusivity in LFN5 enhanced an order magnitude over PNNMO, increasing capacity at high current. Na2/3Ni1/4Mn3/4O2 (NM13) lacks but comparable LFN5. However, NM13 smallest site energy Mn–Mn-coordinated Na compared Ni–Mn higher sites disrupts connectivity Ni–Mn-coordinated These results suggest tuned through control composition, which equal or greater impact on than