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

Cong LEI, Rongzhong YANG, Jianan ZHAO, Wenbin TANG, Fadong MIAO, Qinghong HUANG, Yuping WU

PDF(4741 KB)
PDF(4741 KB)
Front. Energy ›› 2024, Vol. 18 ›› Issue (4) : 436-446. DOI: 10.1007/s11708-024-0928-6
RESEARCH ARTICLE

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

Author information +
History +

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.

Graphical abstract

Keywords

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

Cite this article

Download citation ▾
Cong LEI, Rongzhong YANG, Jianan ZHAO, Wenbin TANG, Fadong MIAO, Qinghong HUANG, Yuping WU. Highly efficient and active Co–N–C catalysts for oxygen reduction and Zn–air batteries. Front. Energy, 2024, 18(4): 436‒446 https://doi.org/10.1007/s11708-024-0928-6

References

[1]
Sun W, Wang F, Zhang B. . A rechargeable Zn–air battery based on Zn peroxide chemistry. Science, 2021, 371(6524): 46–51
CrossRef Google scholar
[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
CrossRef Google scholar
[3]
Chang Q, Xu Y, Zhu S. . Pt–Ni nanourchins as electrocatalysts for oxygen reduction reaction. Frontiers in Energy, 2017, 11(3): 254–259
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[25]
Bian J, Li Z, Li N. . Oxygen deficient LaMn0.75Co0.25O3−δ nanofibers as an efficient electrocatalyst for oxygen evolution reaction and Zn−air batteries. Inorganic Chemistry, 2019, 58(12): 8208–8214
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar
[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
CrossRef Google scholar

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.

RIGHTS & PERMISSIONS

2024 Higher Education Press
AI Summary AI Mindmap
PDF(4741 KB)

Accesses

Citations

Detail

Sections
Recommended

/