Journal of Power Sources, Vol.327, 507-518, 2016
Enhancement of electrochemical performance by simultaneous substitution of Ni and Mn with Fe in Ni-Mn spinel cathodes for Li-ion batteries
LiNi0.5-xFe2xMn1.5-xO4 (x = 0, 0.1, 0.15, 0.2) spinet cathode materials are synthesized using citric acid assisted sol-gel method with final calcination temperature of 1000 degrees C. The structure and morphology of the materials are characterized by using synchrotron and neutron powder diffraction as well as scanning electron microscopy. Different from the parent LiNi0.5Mn1.5O4 (LNMO) material, the Fe-doped spinels do not contain a rock-salt type impurity phase. However, they contain additional layered (C2/m) and spinel Fe3O4 (Fd (3) over barm) phases in small amounts. The substitution of Fe into the spinel structure has been confirmed by Mossbauer spectroscopy. The Fe-doped spinels exhibit improved cycling stability (with a C/2 charge-discharge rate) and rate capability compared to the parent LNMO at room temperature in a voltage range 3.5-5.0 V. Among all these samples, the composition LiNi0.4Fe0.2Mn1.4O4 shows the best room temperature cycling stability (capacity retention of 92% after 300 cycles) as well as the highest initial discharge capacity (134 mAh g(-1)). The delivered capacities at high C-rates (especially at 10C and 20C) with respect to the capacity delivered at C/2 are higher for all Fe-doped samples compared to the parent LNMO. Furthermore, Fe-doping improves the thermal stability of the Ni-Mn spinels in the delithiated state. (C) 2016 Elsevier B.V. All rights reserved.
Keywords:Spinel LiNi0.5Mn1.5O4;Fe-substitution;Cycling stability;Rate capability;Thermal stability;Li-ion batteries