Engineering Ni3+ inside nickel selenide as efficient bifunctional oxygen electrocatalysts for Zn–air batteries

  • Qiu-Ren Pan
  • Si-Jie Li
  • Kaixin Tong
  • Chong Xie
  • Lijuan Peng
  • Nan LiEmail author
  • Dong-Yao Wang
  • Hong SuEmail author
Energy materials


Developing a high-efficienct, low-cost and stable non-noble-metal-based bifunctional electrocatalyst for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) as oxygen electrode material in the rechargeable zinc–air battery is crucial in renewable energy conversion technologies. In this work, nitrogen-doped hollow carbon sphere (NHCS) decorated with various nickel selenide (NixSe) nanoparticles had been designed and successfully prepared. Among them, the Ni0.85Se–NHCS with the highest percentage of Ni3+ could serve as a new efficient bifunctional electrocatalyst toward ORR/OER (with an onset potential of 0.850 V for ORR and a potential of 1.583 V at 10 mA·cm−2 for OER) in an alkaline medium. Furthermore, the assembled Zn–air battery coupled with Ni0.85Se–NHCS electrode has excellent discharging–charging performance and long lifetime. This work provides a valuable understanding on transition metal non-oxide electrocatalysts and expands the applications of selenide-based materials.



This study was funded by Guangzhou municipal Science and Technology Project (No.201607010263), Featured Innovation Project of Guangdong Universities (No. 2017KTSCX142), Undergraduate’s Innovation Training Program (No. 201711078005), and “Climbing” Program of Undergraduate of Guangdong Province (No. pdjh2019b0388).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2019_3520_MOESM1_ESM.docx (2.3 mb)
Supplementary material 1 (DOCX 2332 kb)


  1. 1.
    Liu J, Zhu D, Zheng Y, Vasileff A, Qiao SZ (2018) Self-supported earth-abundant nanoarrays as efficient and robust electrocatalysts for energy-related reactions. ACS Catal 8:6707–6732CrossRefGoogle Scholar
  2. 2.
    Liu ZQ, Cheng H, Li N, Ma TY, Su YZ (2016) ZnCo2O4 quantum dots anchored on nitrogen-doped carbon nanotubes as reversible oxygen reduction/evolution electrocatalysts. Adv Mater 28:3777–3784CrossRefGoogle Scholar
  3. 3.
    Chen X, Zhou Z, Karahan HE, Shao Q, Wei L, Chen Y (2018) Recent advances in materials and design of electrochemically rechargeable zinc–air batteries. Small 14:1801929CrossRefGoogle Scholar
  4. 4.
    Cheng H, Li ML, Su CY, Li N, Liu ZQ (2017) Cu–Co Bimetallic oxide quantum dot decorated nitrogen-doped carbon nanotubes: a high-efficiency bifunctional oxygen electrode for Zn–air batteries. Adv Funct Mater 27:1701833CrossRefGoogle Scholar
  5. 5.
    Gu P, Zheng M, Zhao Q, Xiao X, Xue H, Pang H (2017) Rechargeable zinc–air batteries: a promising way to green energy. J Mater Chem A 5:7651–7666CrossRefGoogle Scholar
  6. 6.
    An L, Zhang Z, Feng J et al (2018) Heterostructure-promoted oxygen electrocatalysis enables rechargeable zinc–air battery with neutral aqueous electrolyte. J Am Chem Soc 140:17624–17631CrossRefGoogle Scholar
  7. 7.
    Swesi AT, Masud J, Nath M (2016) Nickel selenide as a high-efficiency catalyst for oxygen evolution reaction. Energy Environ Sci 9:1771–1782CrossRefGoogle Scholar
  8. 8.
    Guan C, Sumboja A, Wu H et al (2017) Hollow Co3O4 nanosphere embedded in carbon arrays for stable and flexible solid-state zinc–air batteries. Adv Mater 29:1704117CrossRefGoogle Scholar
  9. 9.
    Singh SK, Dhavale VM, Kurungot S (2015) Surface-tuned Co3O4 nanoparticles dispersed on nitrogen-doped graphene as an efficient cathode electrocatalyst for mechanical rechargeable zinc–air battery application. ACS Appl Mater Interfaces 7:21138–21149CrossRefGoogle Scholar
  10. 10.
    Su CY, Cheng H, Li W et al (2017) Atomic modulation of FeCo–nitrogen–carbon bifunctional oxygen electrodes for rechargeable and flexible all-solid-state zinc–air battery. Adv Energy Mater 7:1602420CrossRefGoogle Scholar
  11. 11.
    Li Y, Zhou W, Dong J et al (2018) Interface engineered in situ anchoring of Co9S8 nanoparticles into a multiple doped carbon matrix: highly efficient zinc–air batteries. Nanoscale 10:2649–2657CrossRefGoogle Scholar
  12. 12.
    Yang Y, Zhang K, Lin H, Li X, Chan HC, Yang L, Gao Q (2017) MoS2-Ni3S2 heteronanorods as efficient and stable bifunctional electrocatalysts for overall water splitting. ACS Catal 7:2357–2366CrossRefGoogle Scholar
  13. 13.
    Jiang Q, Chen R, Chen H, Jiang J, Yang X, Ju Y, Ji R, Zhang Y (2018) Improved performance in dye-sensitized solar cells via controlling crystalline structure of nickel selenide. J Mater Sci 53:7672–7682. CrossRefGoogle Scholar
  14. 14.
    Liao M, Zeng G, Luo T, Jin Z, Wang Y, Kou X, Xiao D (2016) Three-dimensional coral-like cobalt selenide as an advanced electrocatalyst for highly efficient oxygen evolution reaction. Electrochim Acta 194:59–66CrossRefGoogle Scholar
  15. 15.
    Gong F, Wang H, Xu X, Zhou G, Wang ZS (2012) In situ growth of Co0.85Se and Ni0.85Se on conductive substrates as high-performance counter electrodes for dye-sensitized solar cells. J Am Chem Soc 134:10953–10958CrossRefGoogle Scholar
  16. 16.
    Zhao Y, Zhang C, Fan R, Li J, Hao Y, He J, Alonso-Vante N, Xue J (2018) Selenium decorated reduced graphene oxide supported CoSe2 nanoparticles as efficient electrochemical catalyst for the oxygen reduction reaction. ChemElectroChem 5:3287–3292CrossRefGoogle Scholar
  17. 17.
    Wang F, Li Y, Shifa TA et al (2016) Selenium-enriched nickel selenide nanosheets as a robust electrocatalyst for hydrogen generation. Angew Chem Int Ed 55:6919–6924CrossRefGoogle Scholar
  18. 18.
    Ge P, Zhang C, Hou H et al (2018) Anions induced evolution of Co3X4 (X = O, S, Se) as sodium-ion anodes: the influences of electronic structure, morphology, electrochemical property. Nano Energy 48:617–629CrossRefGoogle Scholar
  19. 19.
    Peng H, Ma G, Sun K, Zhang Z, Li J, Zhou X, Lei Z (2015) A novel aqueous asymmetric supercapacitor based on petal-like cobalt selenide nanosheets and nitrogen-doped porous carbon networks electrodes. J Power Sources 297:351–358CrossRefGoogle Scholar
  20. 20.
    Zhang L, Sun L, Huang Y, Sun Y, Hu T, Xu K, Ma F (2017) Hydrothermal synthesis of N-doped RGO/MoSe2 composites and enhanced electro-catalytic hydrogen evolution. J Mater Sci 52:13561–13571. CrossRefGoogle Scholar
  21. 21.
    Yuan H, Kong L, Li T, Zhang Q (2017) A review of transition metal chalcogenide/graphene nanocomposites for energy storage and conversion. Chin Chem Lett 28:2180–2194CrossRefGoogle Scholar
  22. 22.
    Yu B, Hu Y, Qi F et al (2017) Nanocrystalline Ni0.85Se as efficient non-noble-metal electrocatalyst for hydrogen evolution reaction. Electrochim Acta 242:25–30CrossRefGoogle Scholar
  23. 23.
    Wang H, Wang X, Yang D, Zheng B, Chen Y (2018) Co0.85Se hollow nanospheres anchored on N-doped graphene nanosheets as highly efficient, nonprecious electrocatalyst for hydrogen evolution reaction in both acid and alkaline media. J Power Sources 400:232–241CrossRefGoogle Scholar
  24. 24.
    Yuan H, Jiao Q, Liu J et al (2017) Facile synthesis of Co0.85Se nanotubes/reduced graphene oxide nanocomposite as Pt-free counter electrode with enhanced electrocatalytic performance in dye-sensitized solar cells. Carbon 122:381–388CrossRefGoogle Scholar
  25. 25.
    Li S, Peng S, Huang L, Cui X, Al-Enizi AM, Zheng G (2016) Carbon-coated Co3+-rich cobalt selenide derived from ZIF-67 for efficient electrochemical water oxidation. ACS Appl Mater Interfaces 8:20534–20539CrossRefGoogle Scholar
  26. 26.
    Wu X, He D, Zhang H et al (2016) Ni0.85Se as an efficient non-noble bifunctional electrocatalyst for full water splitting. Int J Hydrog Energy 41:10688–10694CrossRefGoogle Scholar
  27. 27.
    Ao K, Dong J, Fan C, Wang D, Cai Y, Li D, Huang F, Wei Q (2018) Formation of yolk–shelled nickel–cobalt selenide dodecahedral nanocages from metal–organic frameworks for efficient hydrogen and oxygen evolution. ACS Sustain Chem Eng 6:10952–10959CrossRefGoogle Scholar
  28. 28.
    Zhang H, Yu M, Song H, Noonan O, Zhang J, Yang Y, Zhou L, Yu C (2015) Self-Organized mesostructured hollow carbon nanoparticles via a surfactant-free sequential heterogeneous nucleation pathway. Chem Mater 27:6297–6304CrossRefGoogle Scholar
  29. 29.
    Létiche M, Brousse K, Demortière A et al (2017) Sputtered titanium carbide thick film for high areal energy on chip carbon-based micro-supercapacitors. Adv Funct Mater 27:1606813CrossRefGoogle Scholar
  30. 30.
    Tan L, Yang YD, Li N, Chen S, Liu ZQ (2017) Enhanced activity and stability of Co3O4-decorated nitrogen-doped carbon hollow sphere catalysts for microbial fuel cells. Catal Sci Technol 7:1315–1323CrossRefGoogle Scholar
  31. 31.
    Zhang J, Zhang C, Li W et al (2018) Nitrogen-doped perovskite as a bifunctional cathode catalyst for rechargeable lithium–oxygen batteries. ACS Appl Mater Interfaces 10:5543–5550CrossRefGoogle Scholar
  32. 32.
    Zheng X, Han X, Liu H et al (2018) Controllable synthesis of NixSe (0.5 < x < 1) Nanocrystals for efficient rechargeable zinc–air batteries and water splitting. ACS Appl Mater Interfaces 10:13675–13684CrossRefGoogle Scholar
  33. 33.
    Liu X, Zhai ZY, Chen Z, Zhang LZ, Zhao XF, Si FZ, Li JH (2018) Engineering mesoporous NiO with enriched electrophilic Ni3+ and O toward efficient oxygen evolution. Catalysts 8:310CrossRefGoogle Scholar
  34. 34.
    Tang C, Cheng N, Pu Z, Xing W, Sun X (2015) NiSe Nanowire film supported on nickel foam: an efficient and stable 3D bifunctional electrode for full water splitting. Angew Chem Int Ed 54:9351–9355CrossRefGoogle Scholar
  35. 35.
    Liu J, Zheng Y, Jiao Y, Wang Z, Lu Z, Anthony V, Qiao S (2018) NiO as a bifunctional promoter for RuO2 toward superior overall water splitting. Small 14:1704073CrossRefGoogle Scholar
  36. 36.
    Liu J, Zhu D, Ling T, Anthony V, Qiao S (2017) S-NiFe2O4 ultra-small nanoparticle built nanosheets for efficient water splitting in alkaline and neutral pH. Nano Energy 40:264–273CrossRefGoogle Scholar
  37. 37.
    Wang HY, Hsu YY, Chen R, Chan TS, Chen HM, Liu B (2015) Ni3+-Induced formation of active NiOOH on the spinel Ni–Co oxide surface for efficient oxygen evolution reaction. Adv Energy Mater 5:1500091CrossRefGoogle Scholar
  38. 38.
    Tian GL, Zhao MQ, Yu D, Kong XY, Huang JQ, Zhang Q, Wei F (2014) Nitrogen–doped graphene/carbon nanotube hybrids: in situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction. Small 10:2251–2259CrossRefGoogle Scholar
  39. 39.
    Wang HF, Tang C, Wang B, Li BQ, Zhang Q (2017) Bifunctional transition metal hydroxysulfides: room-temperature sulfurization and their applications in Zn–air batteries. Adv Mater 29:1702327CrossRefGoogle Scholar
  40. 40.
    Tian T, Gao H, Zhou X, Zheng L, Wu J, Li K, Ding Y (2018) Study of the active sites in porous nickel oxide nanosheets by manganese modulation for enhanced oxygen evolution catalysis. ACS Energy Lett 3:2150–2158CrossRefGoogle Scholar
  41. 41.
    Huang Y, Chong X, Liu C, Liang Y, Zhang B (2018) Boosting hydrogen production by anodic oxidation of primary amines over a NiSe nanorod electrode. Angew Chem Int Ed 130:13347–13350CrossRefGoogle Scholar
  42. 42.
    Chaudhari NK, Jin H, Kim B, Lee K (2017) Nanostructured materials on 3D nickel foam as electrocatalysts for water splitting. Nanoscale 9:12231–12247CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Chemistry and Chemical Engineering/Institute of Clean Energy and MaterialsGuangzhou UniversityGuangzhouChina
  2. 2.Institute of Ground Water and Earth SciencesJinan UniversityGuangzhouChina

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