Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries

• Published in: Nanoscale 2014-01, Vol.6 (2), p.986-995
• Main Authors: Wang, Bo, Xu, Binghui, Liu, Tiefeng, Liu, Peng, Guo, Chenfeng, Wang, Shuo, Wang, Qiuming, Xiong, Zhigang, Wang, Dianlong, Zhao, X S
• Format: Article
• Language: English
• Subjects: Electric Power Supplies; Electrochemical Techniques; Electrodes; Graphite - chemistry; Ions - chemistry; Iron - chemistry; Lithium - chemistry; Magnesium - chemistry; Nanostructures - chemistry; Phosphates - chemistry; Porosity
• ISSN: 2040-3372
• DOI: 10.1039/c3nr04611g

In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg(2+) doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg(2+) doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li(+) diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg(2+) doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of "cushion" as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.