Role of local and electronic structural changes with partially anion substitution lithium manganese spinel oxides on their electrochemical properties: X-ray absorption spectroscopy study

• Published in: Dalton transactions : an international journal of inorganic chemistry 2011-10, Vol.40 (38), p.9752-9764
• Main Authors: Okumura, Toyoki, Fukutsuka, Tomokazu, Matsumoto, Keisuke, Orikasa, Yuki, Arai, Hajime, Ogumi, Zempachi, Uchimoto, Yoshiharu
• Format: Article
• Language: English
• Subjects: Anions - chemistry; Electric Power Supplies; Electrochemistry; Electrodes; Electrons; Lithium - chemistry; Manganese - chemistry; Molecular Structure; Oxides - chemical synthesis; Oxides - chemistry; X-Ray Absorption Spectroscopy
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c1dt10612k

The electronic and local structures of partially anion-substituted lithium manganese spinel oxides as positive electrodes for lithium-ion batteries were investigated using X-ray absorption spectroscopy (XAS). LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0, 0.018, 0.036, 0.055, 0.073, 0.110, 0.180) were synthesized by the reaction between LiMn(1.8)Li(0.1)Ni(0.1)O(4) and NH(4)HF(2). The shift of the absorption edge energy in the XANES spectra represented the valence change of Mn ion with the substitution of the low valent cation as Li(+), Ni(2+), or F(-) anion. The local structural change at each compound with the amount of a Jahn-Teller Mn(3+) ion could be observed by EXAFS spectra. The discharge capacity of the tested electrode was in the order of LiMn(2)O(4) > LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0.036) > LiMn(1.8)Li(0.1)Ni(0.1)O(4) while the cycleability was in the order of LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0.036) ≈ LiMn(1.8)Li(0.1)Ni(0.1)O(4) > LiMn(2)O(4). It was clarified that LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) has a good cycleability because of the anion doping effect and simultaneously shows acceptable rechargeable capacity because of the large amount of the Jahn-Teller Mn(3+) ions in the pristine material.