Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (10): 1069-1075.DOI: 10.6023/A20070315 Previous Articles     Next Articles



何锦俊, 张昊喆, 刘晓庆, 卢锡洪   

  1. 中山大学化学学院 生物无机与合成化学教育部重点实验室 广州 510275
  • 投稿日期:2020-07-15 发布日期:2020-09-15
  • 通讯作者: 刘晓庆, 卢锡洪;
  • 基金资助:

Enhancing Zn2+ Storage Capability of Cobalt Manganese Oxide by In-Situ Nanocarbon Coating

He Jinjun, Zhang Haozhe, Liu Xiaoqing, Lu Xihong   

  1. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
  • Received:2020-07-15 Published:2020-09-15
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21822509, U1810110, 21802173) and Science and Technology Planning Project of Guangdong Province (No. 2018A050506028).

The cobalt manganese oxide (CMO), with the advantages of high safety, non-toxicity, easy to obtain, multiple active sites, holds great potential in constructions of Zn-ion batteries (ZIBs). Yet, the dissolution of electrode materials into the electrolyte usually causes the structural collapse during repeated charge/discharge courses, which greatly limits the lifespan of ZIBs and thus restricts their further development. Herein, an in-situ coating method is developed to address this issue. Via a simple one-step hydrothermal method, a nanoscale carbon layer (denoted as nC) is introduced onto the surface of CMO (CMO@C) to prolong its cycling stability. Specifically, 30 mmol NH4F and 75 mmol CO(CH2)2 are first dissolved in 100 mL deionized water. Then, 11.25 mmol Mn(CH3COO)2 and 3.75 mmol Co(CH3COO)2 are added and stirred until the solid completely dissolves. Finally, 0.5 g glucose is dissolved in the solution and stirred for 5 min. The precursor solution is transferred into the 25 mL Teflon-lined stainless-steel autoclave and heated at 125℃ for 6 h in the oven. The as-obtained powder is washed three times by water and then dried at 60℃ overnight. The CMO@C sample is obtained after annealing the powder in air at 450℃ for 1 h. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectra (Raman) characterizations demonstrate that the introduction of the nC coating layer does not alter the composition and structure of CMO. Moreover, taking advantages of the superior conductivity of the carbon coverage, the CMO@C possesses a smaller charge transfer resistance and higher Zn ion diffusion capability compared with the CMO counterpart. The quicker charge transfer and faster ion exchange characteristics are both beneficial to the electrochemical performance optimization, both for the capacity enlargement and for the lifespan extension. As a proof of concept, at the current density of 0.5 A·g-1, the CMO@C shows a high specific capacity of 271.9 mAh·g-1 and no capacity loss is detected after 1000 cycle tests, which substantially outstrip those of the CMO (103.7 mAh·g-1 and 130 cycle lifespan). The work sheds light on the rational design of bimetal oxides as high-performance cathodes for ZIBs assembly.

Key words: Zn-ion battery, in-situ coating, carbon, manganese-base materials, long-term lifespan