Redox mechanism in the binary transition metal phosphide Cu3

The electrochemical behaviour of the binary transition metal phosphide CUR towards lithium is investigated through galvano- and potentiostatic measurements. Obtained through high-temperature synthesis, this system shows a better volumetric capacity than graphite and a good capacity retention. In situ X-ray diffraction and first-principles electronic structure calculations are combined with the electrochemical results to show that the complete insertion of 3Li(+) in the CUR electrode proceeds with the formation of three intermediate phases of lithium composition LixCU(3-x)P (x= 1,2,3). The extra capacity previously observed in discharge is now clearly assigned to lithium insertion into the CuP2 impurity and to SEI reactions. (c) 2006 Elsevier Ltd. All rights reserved.