Cubic imidazolate frameworks-derived CoFe alloy nanoparticles-embedded N-doped graphitic carbon for discharging reaction of Zn-air battery

  • Ziyu Du (杜梓毓)
  • Peng Yu (于鹏)
  • Lei Wang (王蕾)Email author
  • Chungui Tian (田春贵)
  • Xu Liu (刘旭)
  • Guangying Zhang (张光颖)
  • Honggang Fu (付宏刚)Email author


The construction of transition metal-based catalysts with high activity and stability has been widely regarded as a promising method to replace the precious metal Pt for oxygen reduction reaction (ORR). Herein, we synthesized CoFe alloy nanoparticle-embedded N-doped graphitic carbon (CoFe/NC) nanostructures as ORR electrocatalysts. The ZIF-67 (zeolitic imidazolate framework, ZIF) nanocubes were first synthesized, followed by an introduction of Fe2+ ions to form CoFe-ZIF precursors via a simple ion-exchange route. Subsequently, the CoFe/NC composites were synthesized through a facile pyrolysis strategy. The ORR activity and the contents of cobalt and iron could be effectively adjusted by controlling the solution concentration of Fe2+ ions used for the ion exchange and the pyrolysis temperature. The CoFe/NC-0.2-900 composite (synthesized with 0.2 mmol of FeSO4·7H2O at a pyrolysis temperature of 900°C) exhibited ORR activity that was superior to the other samples owing to a synergistic effect of the bimetal, especially considering the extremely high limiting current density of 6.4 mA cm−2 compared with that of Pt/C (5.1 mA cm−2). Rechargeable Zn-air batteries were assembled employing CoFe/NC-0.2-900 and NiFeP/NF (NiFeP supported on nickel foam (NF)) as the catalysts for the discharging and charging processes, respectively, The above materials achieved reduced discharging and charging platforms, high power density, and prolonged cycling stability compared with conventional Pt/C+RuO2/C catalysts.


N-doped graphitic carbon CoFe/NC oxygen reduction reaction Zn-air batteries 

立方体咪唑骨架衍生CoFe合金纳米粒子嵌入N-掺 杂石墨化碳中用于锌空气电池放电反应


目前, 贵金属铂被认为是性能最优异的氧还原催化剂, 但是 其昂贵的价格、有限的储量制约了其大规模应用, 因此制备具有 高催化活性和稳定性的过渡金属基催化剂迫在眉睫. 在本工作中, 我们构筑了一种CoFe合金纳米颗粒嵌入到N-掺杂石墨化碳纳米结 构中的复合材料(CoFe/NC)作为氧还原催化剂. 我们首先制备了 ZIF-67纳米立方体, 再利用离子交换法在其骨架中引入Fe2+形成 CoFe-ZIF前驱体. 通过在惰性气氛下煅烧得到CoFe/NC催化剂. 由 于钴、铁及氮掺杂的协同作用, CoFe/NC-0.2-900催化剂(在900°C 下煅烧掺杂0.2 mmol硫酸亚铁的CoFe/NC)表现出优异的氧还原性 能, 尤其是极限电流密度(6.4 mA cm−2)远高于Pt/C(5.1 mA cm−2). 采用CoFe/NC-0.2-900和NiFeP/NF(负载在泡沫镍上的NiFeP)分别 作为放电和充电反应催化剂组装的可充电锌空气电池, 与传统的 Pt/C+RuO2/C催化剂组装的电池相比, 具有较低的充放电电压差、 较大的功率密度和更优异的循环稳定性.



We gratefully acknowledge the support of the National Natural Science Foundation of China (21771059, 21631004 and 21571054), the Natural Science Foundation of Heilongjiang Province (JJ2019YX0122), Heilongjiang Provincial Postdoctoral Science Foundation (LBH-Q16194) and the excellent Youth Foundation of Heilongjiang University (JC201706).

Author contributions

Du Z designed and performed the experiments; Yu P, Tian C and Liu X discussed partial experimental data. Wang L and Fu H wrote the paper. All authors contributed to the general discussion.

Supplementary material

40843_2019_1190_MOESM1_ESM.pdf (1.5 mb)
Cubic imidazolate frameworks-derived CoFe alloy nanoparticles-embedded N-doped graphitic carbon for discharging reaction of Zn-air battery


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Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Ziyu Du (杜梓毓)
    • 1
  • Peng Yu (于鹏)
    • 1
  • Lei Wang (王蕾)
    • 1
    Email author
  • Chungui Tian (田春贵)
    • 1
  • Xu Liu (刘旭)
    • 1
  • Guangying Zhang (张光颖)
    • 1
  • Honggang Fu (付宏刚)
    • 1
    Email author
  1. 1.Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People’s Republic of ChinaHeilongjiang UniversityHarbinChina

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