Vibrational spectroscopic investigation of structurally-related LiFePO4, NaFePO4, and FePO4 compounds

被引:75
作者
Burba, Christopher M. [1 ]
Frech, Roger [1 ]
机构
[1] Univ Oklahoma, Dept Chem & Biochem, Norman, OK 73019 USA
关键词
vibrational spectroscopy; phospho-olivine materials; cathode materials; Li+ ion batteries;
D O I
10.1016/j.saa.2005.09.025
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
Vibrational spectroscopy was utilized to investigate the local structure of LiFePO4, NaFePO4, and FePO4. The factor group splitting of the intramolecular PO43- vibrations is between 10 and 20 cm(-1) less for NaFePO4 than for LiFePO4. This is because Li+ ions have a higher charge density than Na+ ions and can form stronger coordinative bonds with the PO43- anions. Thus, the internal modes are more perturbed in LiFePO4 and exhibit larger factor group splitting effects. The similarity of the factor group multiplets for both LiFePO4 and NaFePO4, particularly the PO43- bending modes, strongly suggests that the 506 and 470 cm(-1) bands of LiFePO4 consist almost entirely of lithium translatory motion. There are marked differences between the vibrational spectrum of FePO4 and those of LiMPO4 (M = Mn, Fe, Co, or Ni) or NaFePO4. The monovalent cations interact with the oxygen atoms of the phosphate groups, affecting the frequencies and intensities of the intramolecular PO43- modes, in a manner that is absent in FePO4. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:44 / 50
页数:7
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