Li-rich manganese layered oxide is one of the most promising cathode materials that meet the requirements for high-energy-density Li-ion batteries. However, a large irreversible capacity loss at the first cycle makes it difficult to be an applicable cathode material. Although wide investigations have been carried out to overcome such defect, researchers are still beset by the problems of how to concurrently improve the multiple performances of the cathode. In this work, Li[Li0.2Mn0.54Co0.13Ni0.13]O-2 is synthesized, which delivers both improved high-energy capacity of 308 mAh g(-1) and enhanced initial coulombic efficiency of 85%. The corresponding values of a contrast sample are only 245 mAh g(-1) and 77%, respectively. Based on the data of bond distances, crystal cell parameters, and the calculated electron cloud density revealed by Rietveld analysis, an enlarged crystal cell mechanism is proposed. The improved performances are originated from the enlarged crystal cell, which facilitates the Li+ delithiation/lithiation from the octahedral and tetrahedral sites, accordingly increasing the discharge capacity and initial coulombic efficiency. The proposed method offers a strategy to simultaneously increase the initial coulombic efficiency and the specific capacity for Li ion batteries. (C) 2016 Elsevier B.V. All rights reserved.