A series of Al-substituted spinel powders LiNi0.5-xAl2xMn1.5-xO4 (0 <= 2x <= 1.0) have been prepared and the effects of Al concentration on the structural, electrochemical and thermal properties are investigated. The XRD patterns show that impurity arises when 2x >= 0.6. The FTIR and Raman spectra indicate that the introduction of Al in the LiNi0.5Mn1.5O4 increases the disordering degree of Ni/Mn ions, changing the spinel structure from P4(3)32 to Fd (3) over barm. Cyclic voltammetry tests show that the voltage step between Ni2+/Ni3+ and Ni3+/Ni4+ have a sudden leap at 2x = 0.075, responding to the structural difference of the spinels. The Al concentration is optimized in the range of 0.05 <= 2x <= 0.1, in which the cyclic stability and rate capability of the LiNi0.5-xAl2xMn1.5-xO4 spinels are significantly improved. At room temperature the LiNi0.45Al0.10Mn1.45O4 presents the best cycle performance with the capacity retention of 95.4% after 500 cycles at 1C rate, and the best rate capability with the discharge capacity of 119 mAh g(-1) at 10C rate, which is about 93.7% of its capacity at 0.5C. The thermal properties of the spinels have been tested by C80 calorimeter and the results show that introduction of Al in LiNi0.5Mn1.5O4 can effectively suppress the exothermic reaction below 225 degrees C, thus improve the safety of the high voltage cathode material. (C) 2012 Elsevier B.V. All rights reserved.