期刊
JOURNAL OF POWER SOURCES
卷 571, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.jpowsour.2023.233078
关键词
Li-ion Batteries; Phosphates; X-ray Absorption Spectroscopy; Electronic Structure; Cathode Materials; Vanadium Phosphate
Alkali vanadium (III) phosphates show promise as positive electrode materials for Li-, Na-, and K-ion batteries. The reversible redox mechanism of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes during charge/discharge vs. Li+/Li0 has been directly observed using Soft X-ray Absorption Spectroscopy. Surface Li+ insertion is observed for both cathodes after exposure to Li+ electrolyte. The observations provide further understanding of atomic and electronic structure changes and charge-discharge mechanisms of high voltage cathode materials for Li-ion battery applications.
Alkali Vanadium (III) phosphates are a promising class of positive electrode materials for Li-, Na-and K-ion battery applications. Herein, the reversible redox mechanism of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes during charge/discharge vs. Li+/Li0 is directly observed by Soft X-ray Absorption Spectroscopy. For both Li3V2(PO4)3 and Na3V2(PO4)3 spontaneous surface Li + insertion is observed after exposure to Li + electrolyte. Furthermore, for Li3V2(PO4)3 a reversible charge-discharge process is observed from 3.0 V-4.8 V with only slight increase in O contributions to O 2p -V 3d unoccupied hybridised states after charge/discharge vs. Li+/Li0. For Na3V2(PO4)3, persistent VO6 tetrahedral distortion and an accompanying V5+ state is observed, particularly at the surface, after discharge vs. Li+/Li. These observations further elucidate the particular atomic and electronic structure changes and charge-discharge mechanisms of high voltage NASICON and anti-NASICON cathode materials for Li-ion battery applications.
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