General formation of Prussian blue analogue microtubes for high-performance Na-ion hybrid supercapacitors

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  • ReceivedDec 3, 2019
  • AcceptedJan 12, 2020
  • PublishedMar 17, 2020


One-dimensional (1D) hollow-structured nanomaterials with desirable compositions have aroused huge attention in the field of electrochemical energy storage. In the present study, 1D hierarchical cobalt hexacyanoferrate (CoHCF) microtubes were initially fabricated using a facile self-templated method with the electrospun polyacrylonitrile (PAN)-cobalt acetate (Co(Ac)2) as templates. After the chemical reaction was performed between the templates and a potassium ferricyanide solution, the core-shell PAN-Co(Ac)2@CoHCF nanofibers were successfully fabricated. Subsequently, the CoHCF microtubes were finally obtained via the selective dissolution of the PAN-Co(Ac)2 cores. Benefiting from the unique structural characteristic, the CoHCF microtubes electrode exhibited prominent electrochemical characteristics in Na2SO4 aqueous electrolyte, including a high specific capacitance of 281.8 F g−1 (at 1 A g−1), and good rate capability as well as long cycling stability (93% capacitance retention after 5000 cycles). The hybrid supercapacitor assembled with CoHCF microtubes and activated carbon (AC) as the positive and negative electrodes, respectively, exhibited a high energy density of 43.89 W h kg−1, a power density of 27.78 kW kg−1, as well as a long cycle life. Note that this versatile self-templated synthetic strategy could be extended to fabricate other 1D hollow Prussian blue (PB) or its analogues (PBA) with controllable composition, which have a potential application in a range of fields.

Funded by

the National Natural Science Foundation of China(51821091,51872233)

and the Natural Science Foundation of Shaanxi Province(2018JM5044)


This work was supported by the National Natural Science Foundation of China (51821091 and 51872233), and the Natural Science Foundation of Shaanxi Province (2018JM5044). We would like to thank the Analytical & Testing Center of Northwestern Polytechnical University for the morphology characterizations.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Yin X, Li H and Lu J designed the experiments. Yin X and Yuan R performed the material characterizations. Yin X wrote the paper with support from Zhang L. All authors contributed to the general discussion.

Author information

Xuemin Yin is currently a PhD student at the School of Materials Science and Engineering, Northwestern Polytechnical University. His research focuses on the nanomaterials for electrochemical energy storage.

Hejun Li is a professor at the School of Materials Science and Engineering, Northwestern Polytechnical University. He received his PhD degree from Harbin Institute of Technology in 1991. His current research interests include advanced carbon/carbon composites, anti-oxidation coatings, paper based friction materials and nanomaterials.

Jinhua Lu is an associate professor at the School of Materials Science and Engineering, Northwestern Polytechnical University. Her current research interests include carbon/carbon composites and nanomaterials.


Supplementary information

Supporting data are available in the online version of the paper.


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  • Figure 1

    Schematic illustration of the synthesis procedure of CoHCF hollow microtubes using electrospun PAN-Co(Ac)2 nanofibers as the templates. I, the preparation of PAN-Co(Ac)2 nanofiber templates by electrospinning; II, the growth of CoHCF on the PAN-Co(Ac)2 nanofibers; III, selective etching of the PAN-Co(Ac)2 cores in DMF solution.

  • Figure 2

    (a–c) SEM images, (d) TEM image, (e) HRTEM image, (f) SEAD pattern and (g) EDX mappings of the synthesized CoHCF microtubes.

  • Figure 3

    (a) XRD pattern and (b) FT-IR spectrum, and (c–f) XPS spectra of the synthesized CoHCF microtubes. (c) Survey scan spectrum; high-resolution spectra of (d) C 1s, (e) N 1s and (f) Fe 2p and Co 2p.

  • Figure 4

    (a, d) FESEM, (b, e) TEM images and (c, f) XRD patterns of (a–c) NiHCF and (d–f) MnHCF microtubes.

  • Figure 5

    (a) CV curves of the CoHCF microtubes at various scan rates. (b) GCD curves at various current densities. (c) The specific capacitance as a function of current density. (d) Cycling performance at a current density of 5 A g−1.

  • Figure 6

    (a) CV curves of CoHCF and AC electrodes at a scan rate of 20 mV s−1. (b) CV curves of the CoHCF//AC hybrid device at various scan rates. (c) GCD curves at different current densities. (d) The specific capacitance as a function of the current density. (e) Cycling stability and (f) Ragone plots of the CoHCF//AC hybrid devices.

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