화학공학소재연구정보센터
Journal of Power Sources, Vol.315, 269-276, 2016
Variations in structure and electrochemistry of iron- and titanium-doped lithium nickel manganese oxyfluoride spinels
Doping of cathode materials can considerably improve electrochemical performance and stability. Here, the high-voltage LiNi0.5Mn1.5O4 spinel is used as a candidate material. It is high-voltage cycling at a potential of approximately 4.7 V and the ability to host 2 eq. Li, thus leading to a theoretical capacity of 294 mAh g(-1), that makes this material interesting. In order to improve stability and electronic conductivity, the spinel is doped with titanium and iron. Cycling in a voltage range of 2.0-5.0 V leads to a cooperative Jahn-Teller distortion accompanied by a phase transformation from cubic to tetragonal symmetry. This causes a severe capacity fade. To improve capacity retention, the as-prepared spinel is post-doped with fluorine. Influence of different fluorine amounts in LiNi0.5Mn1.4Fe0.1Ti0.027O4-xFx (x = 0-03) on the capacity and stability is analyzed. The initial capacities decrease with increasing fluorine content but the low voltage capacity is stabilized. Best electrochemical results are obtained with a fluorine content of x = 0.15. Furthermore, an additional redox couple is found. The intensity of this depends on the fluorine content. It is assumed that manganese, either in the tetrahedral sites or in octahedral sites, bound to fluorine lead to a higher voltage. (C) 2016 Elsevier B.V. All rights reserved.