TY - JOUR
T1 - A novel NASICON-Na3.4MnV0.2Cr0.2Ti0.6(PO4)3 cathode with ultrahigh energy density and remarkable cycling stability toward practical Na-ion batteries
AU - Fan, Dashan
AU - Wang, Yao
AU - Zhao, Xudong
AU - Jin, Junteng
AU - Shen, Qiuyu
AU - Li, Zhenyou
AU - Qu, Xuanhui
AU - Jiao, Lifang
AU - Liu, Yongchang
AU - Guo, Zaiping
PY - 2025/7
Y1 - 2025/7
N2 - The pursuit of an advanced cathode material featuring high energy density and long lifespan is of great significance to promote the practical applications of sodium-ion batteries (SIBs). Herein, a novel Na superionic conductor (NASICON)-type Na3.4MnV0.2Cr0.2Ti0.6(PO4)3/C (NMVCTP/C) cathode is developed, the active Ti3+/Ti4+, V3+/V4+/V5+, Mn2+/Mn3+/Mn4+, and Cr3+/Cr4+ redox couples endow the cathode with an extraordinary discharge capacity of 176.7 mAh g−1 (3.1-electron transfer) and a high output voltage of 3.47 V, harvesting a record-high practical energy density of 613.15 Wh kg−1 for the polyanionic cathodes for SIBs. The reversible bi-phase and solid-solution reaction with a small volume change of 5.5 % during the multi-electron charge/discharge process is systematically expounded by in-situ X-ray diffraction, ex-situ X-ray absorption spectroscopy and 23Na nuclear magnetic resonance analyses. Besides, theoretical computations elucidate that Cr doping could enhance the V4+/V5+ reaction reversibility by suppressing the V migration to Na site. Consequently, the NMVCTP/C cathode affords an admirable cycling stability of 92.4 % capacity retention after 2000 cycles. More excitingly, a 3.75 Ah pouch cell is successfully constructed employing the NMVCTP/C cathode and hard carbon anode, demonstrating considerable application prospects. This study upgrades the energy density of polyanion-type Na-storage cathodes to a new level by rationally modulating redox couples. © 2025 Elsevier Ltd.
AB - The pursuit of an advanced cathode material featuring high energy density and long lifespan is of great significance to promote the practical applications of sodium-ion batteries (SIBs). Herein, a novel Na superionic conductor (NASICON)-type Na3.4MnV0.2Cr0.2Ti0.6(PO4)3/C (NMVCTP/C) cathode is developed, the active Ti3+/Ti4+, V3+/V4+/V5+, Mn2+/Mn3+/Mn4+, and Cr3+/Cr4+ redox couples endow the cathode with an extraordinary discharge capacity of 176.7 mAh g−1 (3.1-electron transfer) and a high output voltage of 3.47 V, harvesting a record-high practical energy density of 613.15 Wh kg−1 for the polyanionic cathodes for SIBs. The reversible bi-phase and solid-solution reaction with a small volume change of 5.5 % during the multi-electron charge/discharge process is systematically expounded by in-situ X-ray diffraction, ex-situ X-ray absorption spectroscopy and 23Na nuclear magnetic resonance analyses. Besides, theoretical computations elucidate that Cr doping could enhance the V4+/V5+ reaction reversibility by suppressing the V migration to Na site. Consequently, the NMVCTP/C cathode affords an admirable cycling stability of 92.4 % capacity retention after 2000 cycles. More excitingly, a 3.75 Ah pouch cell is successfully constructed employing the NMVCTP/C cathode and hard carbon anode, demonstrating considerable application prospects. This study upgrades the energy density of polyanion-type Na-storage cathodes to a new level by rationally modulating redox couples. © 2025 Elsevier Ltd.
KW - Cathode materials
KW - Energy density
KW - Multi-electron reactions
KW - Polyanionic compounds
KW - Sodium-ion batteries
UR - https://www.scopus.com/pages/publications/105000599535
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-105000599535&origin=recordpage
U2 - 10.1016/j.mattod.2025.03.010
DO - 10.1016/j.mattod.2025.03.010
M3 - RGC 21 - Publication in refereed journal
SN - 1369-7021
VL - 86
SP - 63
EP - 73
JO - Materials Today
JF - Materials Today
ER -
SDG 7 Affordable and Clean Energy