Impact of Ti and Zn Dual‐Substitution in P2 Type Na2/3Ni1/3Mn2/3O2 on Ni–Mn and Na‐Vacancy Ordering and Electrochemical Properties

• Published in: Advanced materials (Weinheim) Vol. 35; no. 26
• Main Authors: Kubota, Kei, Asari, Takuya, Komaba, Shinichi
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 28-06-2023
• Subjects: cathode materials; Electrochemical analysis; Electrode materials; Electron diffraction; intercalation; layered oxides; Materials science; Sodium; sodium batteries; Sodium-ion batteries; Step voltage; structural analysis; Substitutes; substitution; superstructure; Synchrotrons; Titanium; Transition metals
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202300714

High‐entropy layered oxide materials containing various metals that exhibit smooth voltage curves and excellent electrochemical performances have attracted attention in the development of positive electrode materials for sodium‐ion batteries. However, a smooth voltage curve can be obtained by suppression of the Na+‐vacancy ordering, and therefore, transition metal slabs do not need to be more multi‐element than necessary. Here, the Na+‐vacancy ordering is found to be disturbed by dual substitution of TiIV for MnIV and ZnII for NiII in P2‐Na2/3[Ni1/3Mn2/3]O2. Dual‐substituted Na2/3[Ni1/4Mn1/2Ti1/6Zn1/12]O2 demonstrates almost non‐step voltage curves with a reversible capacity of 114 mAh g−1 and less structural changes with a high crystalline structure maintained during charging and discharging. Synchrotron X‐ray, neutron, and electron diffraction measurements reveal that dual‐substitution with TiIV and ZnII uniquely promotes in‐plane NiII–MnIV ordering, which is quite different from the disordered mixing in conventional multiple metal substitution.
Dual‐substitution by Ti and Zn for Mn and Ni, respectively, in P2 type Na2/3Ni1/3Mn2/3O2 maintains in‐plane Ni–Mn ordering but disrupts Na+‐vacancy ordering, resulting in long‐cycling‐life non‐aqueous Na cells with smooth charge–discharge voltage curves and little structural change from the P2‐type layered structure.