Journal
JOURNAL OF POWER SOURCES
Volume 521, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.jpowsour.2021.230922
Keywords
Sodium ion batteries; Na4Fe2.7Mn0.3(PO4)(2)P2O7/rGO,Mn2+ doping; Carbon coating; DFT computations
Funding
- National Natural Science Foundation of China [21975155, 21938005]
- Science and Technology Com-mission of Shanghai Municipality [19DZ2271100]
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In this study, a manganese-doped sodium ion battery cathode material Na4Fe2.7Mn0.3(PO4)(2)P2O7/rGO (Mn0.3-NFPP/rGO) with graphene modification was proposed, which successfully improved the conductivity and cycle stability of the material, and exhibited excellent rate performance and low-temperature performance. Density functional theory calculations showed that manganese doping helped to improve Na+ diffusion kinetics and conductivity, and enhance the structural stability during long cycling.
Na4Fe3(PO4)(2)P2O7(NFPP) is known as a cathode material with great potential for sodium ion batteries (SIBs) due to its thermodynamic stability, considerable theoretical capacity and small volume change. However, its inherent poor conductivity leads to low discharge capacity and poor cycle stability, which greatly limits its widespread and practical application. In this work, a Mn2+ doped NFPP together with the graphene modification, is proposed. It is found that the optimal Na4Fe2.7Mn0.3(PO4)(2)P2O7/rGO(Mn0.3-NFPP/rGO) can provide an initial discharge capacity of 131.5 mAh g(-1) at 0.1C, (1C = 129mAh g(-1)) also an excellent rate performance (70.2 mAh g(-1) at 50C) and good long cycle stability (97.2% capacity retention after 2000 cycles at 10C) can be obtained. Impressively, the as-prepared Mn0.3-NFPP/rGO also shows excellent low-temperature performance, at -20 degrees C, it demonstrates a discharge capacity of 85.3 mAh g(-1) at 0.2C and good rate performance. Density functional theory (DFT) calculation shows that Mn2+ doping reduces the Na+ migration energy barrier, and also narrows the bandgap of the NFPP lattice, which is beneficial to improve the Na+ diffusion kinetics and conductivity. In addition, the doping of Mn2+ can further help to improve its structural stability during the long cycling process.
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