Highly efficient and active Co–N–C catalysts for oxygen reduction and Zn–air batteries

Abstract

In this study, the Lewis doping approach of polyaniline (PANI) was employed to fabricate cobait–nitrogen–carbon (Co–N–C) oxygen electrocatalysts for Zn–air batteries, aiming to enhance the active spots of Co–N–C. This resulting Co–N–C catalysts exhibited well-defined nanofiber networks, and the Brunauer-Emmett-Teller (BET) analysis confirmed their substantial specific surface area. Electrochemical experiments demonstrated that the Co–N–C catalysts achieved the half-wave potential (vs. RHE) of 0.85 V in alkaline medium, overcoming Pt/C and iron–nitrogen–carbon (Fe–N–C) counterparts in extended cycle testing with only a 25 mV change in a half-wave potential after 5000 cycles. Remarkably, the highest power density measured in the zinc (Zn)-air battery reached 227 mW/cm², a significant improvement over the performance of 101 mW/cm² of the platinum on activated carbon (Pt/C) catalyst. These findings highlight the advantageous stability enhancement associated with the utilization of Co in the Co–N–C catalysts.

Key words： oxygen reduction reaction (ORR); oxygen evolution reaction (OER); non-noble metal catalysts; Co–N–C catalysts; Zn–air battery

Acknowledgements

This work was partially supported by the National Natural Science Foundation of China (Grant No. 22279054).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-024-0928-6 and is accessible for authorized users.

Competing interests

The authors declare that they have no competing interests.

References

1 Sun W, Wang F, Zhang B. . A rechargeable Zn–air battery based on Zn peroxide chemistry. Science, 2021, 371(6524): 46–51

2 Zhang W, Xu C, Zheng H. . Oxygen-rich cobalt–nitrogen–carbon porous nanosheets for bifunctional oxygen electrocatalysis. Advanced Functional Materials, 2022, 32(23): 2200763

3 Chang Q, Xu Y, Zhu S. . Pt–Ni nanourchins as electrocatalysts for oxygen reduction reaction. Frontiers in Energy, 2017, 11(3): 254–259

4 Zhang X, Zhu Z, Tan Y. . Co, Fe co-doped holey carbon nanosheets as bifunctional oxygen electrocatalysts for rechargeable Zn–air batteries. Chemical Communications, 2021, 57(16): 2049–2052

5 Ma F, Xiong Y, Fan H. . Protruding N-doped carbon nanotubes on elongated hexagonal Co–N–C nanoplates as bifunctional oxygen electrocatalysts for Zn–air batteries. Materials Chemistry Frontiers, 2023, 7(5): 946–954

6 Zhou W, Li Y, Zheng L. . Three-dimensional MOF-derived Co and N co-doped porous carbon bifunctional catalyst for the Zn–air battery. CrystEngComm, 2021, 23(28): 4930–4937

7 Zhang C, Shen X, Pan Y. . A review of Pt-based electrocatalysts for oxygen reduction reaction. Frontiers in Energy, 2017, 11(3): 268–285

8 Liu J, Guo Y, Fu X. . Strengthening absorption ability of Co–N–C as efficient bifunctional oxygen catalyst by modulating the d band center using MoC. Green Energy & Environment, 2023, 8(2): 459–469

9 Li L, Fu C, Shen S. . Influence of Fe on electrocatalytic activity of iron–nitrogen–doped carbon materials toward oxygen reduction reaction. Frontiers in Energy, 2022, 16(5): 812–821

10 Zhu J, Mu S. Active site engineering of atomically dispersed transition metal–heteroatom–carbon catalysts for oxygen reduction. Chemical Communications, 2021, 57(64): 7869–7881

11 Wang W, Jia Q, Mukerjee S. . Recent insights into the oxygen-reduction electrocatalysis of Fe/N/C materials. ACS Catalysis, 2019, 9(11): 10126–10141

12 Wang Y, Wang D, Li Y. Rational design of single-atom site electrocatalysts: From theoretical understandings to practical applications. Advanced Materials, 2021, 33(34): 2008151

13 Cui J, Chen Q, Li X. . Recent advances in non-precious metal electrocatalysts for oxygen reduction in acidic media and PEMFCs: An activity, stability and mechanism study. Green Chemistry, 2021, 23(18): 6898–6925

14 Ma L, Chen S, Pei Z. . Single-site active iron-based bifunctional oxygen catalyst for a compressible and rechargeable Zn–air battery. ACS Nano, 2018, 12(2): 1949–1958

15 Wang X, Cullen D A, Pan Y. . Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells. Advanced Materials, 2018, 30(11): 1706758

16 Meng X, Han J, Lu L. . Fe²⁺-doped layered double (Ni, Fe) hydroxides as efficient electrocatalysts for water splitting and self-powered electrochemical systems. Small, 2019, 15(41): 1902551

17 Hao Y, Kang Y, Mi Y. . Highly ordered micro-meso-macroporous Co–N-doped carbon polyhedrons from bimetal-organic frameworks for rechargeable Zn–air batteries. Journal of Colloid and Interface Science, 2021, 598: 83–92

18 Yang S, Xue X, Liu X. . Scalable synthesis of micromesoporous iron–nitrogen–doped carbon as highly active and stable oxygen reduction electrocatalyst. ACS Applied Materials & Interfaces, 2019, 11(42): 39263–39273

19 Zhang D, Sun P, Zhou Q. . Enhanced oxygen reduction and evolution in N-doped carbon anchored with Co nanoparticles for rechargeable Zn–air batteries. Applied Surface Science, 2021, 542: 148700

20 Chen D, Pan L, Pei P. . Cobalt-based oxygen electrocatalysts for Zn–air batteries: Recent progress, challenges, and perspectives. Nano Research, 2022, 15(6): 5038–5063

21 Bian J, Cheng X, Meng X. . Nitrogen-doped NiCo₂O₄ microsphere as an efficient catalyst for flexible rechargeable Zn–air batteries and self-charging power system. ACS Applied Energy Materials, 2019, 2(3): 2296–2304

22 Feng Q, Zhao S, Xu Q. . Mesoporous nitrogen-doped carbon-nanosphere-supported isolated single-atom Pd catalyst for highly efficient semihydrogenation of acetylene. Advanced Materials, 2019, 31(36): 1901024

23 Chen L, Liu X, Zheng L. . Insights into the role of active site density in the fuel cell performance of Co–N–C catalysts. Applied Catalysis B: Environmental, 2019, 256: 117849

24 Han X, Ling X, Wang Y. . Generation of nanoparticle, atomic-cluster, and single-atom cobalt catalysts from zeolitic imidazole frameworks by spatial isolation and their use in Zn–air batteries. Angewandte Chemie International Edition, 2019, 58(16): 5359–5364

25 Bian J, Li Z, Li N. . Oxygen deficient LaMn_0.75Co_0.25O_3−δ nanofibers as an efficient electrocatalyst for oxygen evolution reaction and Zn−air batteries. Inorganic Chemistry, 2019, 58(12): 8208–8214

26 Zhou X, Gao J, Hu Y. . Theoretically revealed and experimentally demonstrated synergistic electronic interaction of CoFe dual-metal sites on N-doped carbon for boosting both oxygen reduction and evolution reactions. Nano Letters, 2022, 22(8): 3392–3399

27 Zhang J, Dai L. Nitrogen, phosphorus, and fluorine tri-doped graphene as a multifunctional catalyst for self-powered electrochemical water splitting. Angewandte Chemie International Edition, 2016, 55(42): 13296–13300

28 Zhou Y, Yen C, Hu Y. . Making ultrafine and highly-dispersive multimetallic nanoparticles in three-dimensional graphene with supercritical fluid as excellent electrocatalyst for oxygen reduction reaction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(47): 18628–18638

29 Li Y, Zhong C, Liu J. . Atomically thin mesoporous Co₃O₄ layers strongly coupled with N-rGO nanosheets as high-performance bifunctional catalysts for 1D knittable Zn–air batteries. Advanced Materials, 2018, 30(4): 1703657

30 Li Y, Wen H, Yang J. . Boosting oxygen reduction catalysis with N, F, and S tri-doped porous graphene: Tertiary N-precursors regulates the constitution of catalytic active sites. Carbon, 2019, 142: 1–12

31 Tran H D, D’Arcy J M, Wang Y. . The oxidation of aniline to produce “polyaniline”: A process yielding many different nanoscale structures. Journal of Materials Chemistry, 2011, 21(11): 3534–3550

32 Mondal S, Malik S. Easy synthesis approach of Pt-nanoparticles on polyaniline surface: An efficient electro-catalyst for methanol oxidation reaction. Journal of Power Sources, 2016, 328: 271–279

33 He Y, Hwang S, Cullen D A. . Highly active atomically dispersed CoN₄ fuel cell cathode catalysts derived from surfactant-assisted MOFs: Carbon-shell confinement strategy. Energy & Environmental Science, 2019, 12(1): 250–260

34 Li X, Zhou T, Luo Z. . N, S heteroatom co-doped carbon-based materials carrying Mn and Co atoms as bifunctional catalysts for stable rechargeable Zn–air batteries. Journal of Alloys and Compounds, 2023, 939: 168756

35 Cai J, Zhou Q, Liu B. . A sponge-templated sandwich-like cobalt-embedded nitrogen-doped carbon polyhedron/graphene composite as a highly efficient catalyst for Zn–air batteries. Nanoscale, 2020, 12(2): 973–982

36 Quílez-Bermejo J, Gonzalez-Gaitan C, Morallon E. . Effect of carbonization conditions of polyaniline on its catalytic activity towards ORR. Some insights about the nature of the active sites. Carbon, 2017, 119: 62–71

37 Zhu Y, Zhang Z, Lei Z. . Defect-enriched hollow porous Co–N-doped carbon for oxygen reduction reaction and Zn–air batteries. Carbon, 2020, 167: 188–195

38 Lee S H, Kim J, Chung D, et al. Design principle of Fe–N–C electrocatalysts: How to optimize multimodal porous structures? Journal of the American Chemical Society, 2019, 141(5): 2035–2045 10.1021/jacs.8b11129

39 Kim S, Park H, Li O. Cobalt nanoparticles on plasma-controlled nitrogen-doped carbon as high-performance ORR electrocatalyst for primary Zn–air battery. Nanomaterials, 2020, 10(2): 223

40 Ikeda T, Boero M, Huang S. . Carbon alloy catalysts: Active sites for oxygen reduction reaction. Journal of Physical Chemistry C, 2008, 112(38): 14706–14709

41 Liu R, Wu D, Feng X. . Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angewandte Chemie International Edition, 2010, 49(14): 2565–2569

42 Ratso S, Kruusenberg I, Vikkisk M. . Highly active nitrogen-doped few-layer graphene/carbon nanotube composite electrocatalyst for oxygen reduction reaction in alkaline media. Carbon, 2014, 73: 361–370

43 Ratso S, Kruusenberg I, Joost U. . Enhanced oxygen reduction reaction activity of nitrogen-doped graphene/multi-walled carbon nanotube catalysts in alkaline media. International Journal of Hydrogen Energy, 2016, 41(47): 22510–22519

44 Wu S, Witten I H, Franken M. Utilizing lexical data from a web-derived corpus to expand productive collocation knowledge. ReCALL, 2010, 22(1): 83–102

45 Zhou R, Zheng Y, Jaroniec M. . Determination of the electron transfer number for the oxygen reduction reaction: From theory to experiment. ACS Catalysis, 2016, 6(7): 4720–4728

46 Zhao C X, Liu J N, Wang J. . A ΔE = 0.63 V bifunctional oxygen electrocatalyst enables high-rate and long-cycling Zn–air batteries. Advanced Materials, 2021, 33(15): 2008606

47 Wan X, Guo X, Duan M. . Ultrafine CoO nanoparticles and Co–N–C lamellae supported on mesoporous carbon for efficient electrocatalysis of oxygen reduction in Zn–air batteries. Electrochimica Acta, 2021, 394: 139135

48 Liu T, Mou J, Wu Z. . A facile and scalable strategy for fabrication of superior bifunctional freestanding air electrodes for flexible Zn–air batteries. Advanced Functional Materials, 2020, 30(36): 2003407

49 Wang T, Liu M, Chaemchuen S. . Constructing a stable cobalt-nitrogen-carbon air cathode from coordinatively unsaturated zeolitic-imidazole frameworks for rechargeable Zn–air batteries. Nano Research, 2022, 15(7): 5895–5901

50 Qin J, Liu Z, Wu D. . Optimizing the electronic structure of cobalt via synergized oxygen vacancy and Co–N–C to boost reversible oxygen electrocatalysis for rechargeable Zn–air batteries. Applied Catalysis B: Environmental, 2020, 278: 119300

51 Ma Y, Chen D, Li W. . Highly dispersive Co@N–C catalyst as freestanding bifunctional cathode for flexible and rechargeable Zn–air batteries. Energy & Environmental Materials, 2022, 5(2): 543–554

52 Jiang B, Liu X, Wang F. . A facile approach to efficiently load and isolate CoN active sites for the preparation of a high-performance Co–N–C oxygen reduction catalyst. Energy Technology, 2023, 11(4): 2201399

53 Yang W, Guo J, Ma J. . FeCo nanoalloys encapsulated in N-doped carbon nanofibers as a trifunctional catalyst for rechargeable Zn–air batteries and overall water electrolysis. Journal of Alloys and Compounds, 2022, 926: 166937