A Novel NASICON‐Typed Na4VMn0.5Fe0.5(PO4)3 Cathode for High‐Performance Na‐Ion Batteries

• Published in: Advanced energy materials 2021-06, Vol.11 (22), p.n/a
• Main Authors: Xu, Chunliu, Zhao, Junmei, Wang, Enhui, Liu, Xiaohong, Shen, Xing, Rong, Xiaohui, Zheng, Qiong, Ren, Guoxin, Zhang, Nian, Liu, Xiaosong, Guo, Xiaodong, Yang, Chao, Liu, Huizhou, Zhong, Benhe, Hu, Yong‐Sheng
• Format: Article
• Language: English
• Subjects: Cathodes; Conductors; Na 3V 2(PO 4) 3; Na 4VMn 0.5Fe 0.5(PO 4) 3; NASICON; Oxidation; Rechargeable batteries; Sodium; Sodium-ion batteries; Structural stability; substitution; Substitution reactions; synergetic contributions; Vanadium
• ISSN: 1614-6832; 1614-6840
• DOI: 10.1002/aenm.202100729

The Na+ superionic conductor (NASICON)‐type Na3V2(PO4)3 cathodes have attracted extensive interest due to their high structural stability and fast Na+ mobility. However, the substitution of vanadium with low‐cost active elements remains imperative due to high cost of vanadium, to further boost its application feasibility. Herein, a novel ternary NASICON‐type Na4VMn0.5Fe0.5(PO4)3/C cathode is designed, which integrates the advantages of large reversible capacity, high voltage, and good stability. The as‐obtained Na4VMn0.5Fe0.5(PO4)3/C composite can deliver an excellent rate capacity of 96 m Ah g‐1 at 20 C and decent cycling durability of 94% after 3000 cycles at 20 C, which is superior to that of Na4VFe(PO4)3/C and Na4VMn(PO4)3/C. The synergetic contributions of multimetal ions and facilitated Na+ migration of the Na4VMn0.5Fe0.5(PO4)3/C cathode are confirmed by the first‐principles calculations. The processive reduction/oxidation involved in Fe2+/Fe3+, Mn2+/Mn3+, V3+/V4+/V5+ redox couples are also revealed upon the charging/discharging process by ex situ soft X‐ray absorption spectroscopy. The reversible structure evolution and small volume change during the electrochemical reaction is demonstrated by in situ X‐ray diffraction characterization. The rational design of NASICON‐type cathodes by regulating composition with substitution of multimetal ions can provide new perspectives for high‐performance Na‐ion batteries. A novel ternary phosphate cathode is developed with an in situ graphitized carbon coating, Na4VMn0.5Fe0.5(PO4)3/C, which integrates the advantages of individual V, Fe, Mn, and synergetic contributions from multimetal ions. Benefiting from the unique carbon framework architecture and rational composition design, the optimized cathode shows excellent electrochemical performance.