Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (2): 150-158.DOI: 10.6023/A21100477 Previous Articles     Next Articles



黄擎a,b, 丁瑞a,b, 陈来a,b,*(), 卢赟a,b, 石奇a,b, 张其雨a,b, 聂启军a,b, 苏岳锋a,b,*(), 吴锋a,b   

  1. a 北京理工大学材料学院环境科学与工程北京市重点实验室 北京 100081
    b 北京理工大学重庆创新中心 重庆 401120
  • 投稿日期:2021-10-26 发布日期:2022-01-18
  • 通讯作者: 陈来, 苏岳锋
  • 基金资助:
    国家自然科学基金(2217090605); 国家自然科学基金(21875022); 国家自然科学基金(51802020); 重庆市自然科学基金(cstc2020jcyj-msxmX0654); 重庆市自然科学基金(cstc2020jcyj-msxmX0589); 中国科学技术协会青年人才托举计划(2018QNRC001); 北京理工大学“青年教师学术启动计划”

Dual-Decoration and Mechanism Analysis of Ni-rich LiNi0.83Co0.11Mn0.06O2 Cathodes by Na2PO3F

Qing Huanga,b, Rui Dinga,b, Lai Chena,b(), Yun Lua,b, Qi Shia,b, Qiyu Zhanga,b, Qijun Niea,b, Yuefeng Sua,b(), Feng Wua,b   

  1. a School of Materials Science and Engineering, Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081
    b Beijing Institute of Technology Chongqing Innovation Center, Chongqing 401120
  • Received:2021-10-26 Published:2022-01-18
  • Contact: Lai Chen, Yuefeng Su
  • Supported by:
    National Natural Science Foundation of China(2217090605); National Natural Science Foundation of China(21875022); National Natural Science Foundation of China(51802020); Natural Science Foundation of Chongqing, China(cstc2020jcyj-msxmX0654); Natural Science Foundation of Chongqing, China(cstc2020jcyj-msxmX0589); Young Elite Scientists Sponsorship Program by China Association for Science and Technology, China(2018QNRC001); L. Chen acknowledges the support from Beijing Institute of Technology Research Fund Program for Young Scholars

Since the commercialization of lithium-ion battery in 1991, it has promoted human society development for nearly three decades. Due to its higher energy density, Ni-rich layered oxides currently stand out as the most promising cathode materials to build power batteries for portable electronic devices and new energy electric vehicles. However, the severe side effects on the electrode/electrolyte interface and the structural instability of the material hinder its development, and a lot of research focus on improving the cycling stability and rate capability of nickel-rich cathode material. Here, a facile treatment with Na2PO3F was carried out to modify the Ni-rich LiNi0.83Co0.11Mn0.06O2 material at surface and bulk regions by using wet methods. By virtue of the fact that Na2PO3F dissolves in water and releases fluorine ions, a F doped and LiF coated Ni-rich LiNi0.83Co0.11Mn0.06O2 material was obtained. The X-ray diffraction (XRD) results showed that (003) peak shifted to a higher angle due to the replacement of O2– by smaller F. Besides, the XRD Rietveld refinement and X-ray photoelectron spectroscopy (XPS) sputtering data determined that part of F ions had been successfully doped into the lattice, and the basic layer structure of the material was still well preserved in the process of modification. Scanning electron microscope (SEM), energy disperse spectroscopy (EDS), and transmission electron microscope (TEM) combined with XPS proved the existence of surface LiF coating layer. The 2~10 nm LiF layer was uniformly covered onto the surface of the cathode material, acting as a physical barrier against direct corrosion from the electrolyte, thus enhancing the cycling stability. In addition, the lithium ion diffusion coefficients (DLi+) for bare and modified samples were calculated from cyclic voltammetry test results, which reveals a better rate capability from the synergistic effect of surface LiF coating and lattice F doping. The electrochemical tests also showed a better cycling stability and enhanced rate capability of the modified samples: within 2.75~4.3 V, the capacity retention after 200 cycles at 1 C-rate had been elevated from 32.2% to 65.2%; the discharge capacity under 10 C-rate was also improved from 145.7 to 161.5 mAh/g. To elaborate the improved effect, post-cycling characterizations were conducted. The morphology of modified particles after 200 cycles at 1 C still maintained intact grains, in contrast with the bare samples, exhibiting many micro-cracks. XPS spectra on decorated cathodes after cycling showed weaker signals of by-products including LiF, LixPOyFz, NiF2 in the CEI layer, indicating side reaction on the interface was effectively suppressed, thus contributing to enhancing the cycling stability. The applicable method herein demonstrates a promising solution for improvement of Ni-rich cathode materials and their coming commercial application.

Key words: lithium-ion batteries, nickel-rich cathode, LiF coating, F doping, cycling stability, rate performance