Skip to main content

Advertisement

SpringerLink
Log in

Fe, P, N, S multidoping porous graphene material as a Bifunctional OER/ORR electrocatalytic activity for enhancing rechargeable Zn-air batteries

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

Oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) electrocatalyst activity may be regarded as a crucial indicator of expected performance in metal-air batteries, which are limited by the inadequate electrochemical activity and low conductivity of accessible materials. This disadvantage can be solved by the development of hierarchically structured three-dimensional (3D) carbon. Through carbonization method, we synthesize the bifunctional catalysts, Fe, P, N, and S multidoped porous graphene (FePNS-G) for use in rechargeable Zn–air batteries (ZABs). FePNS-G-2 indicates superior active site density for both the OER and ORR. Moreover, the FePNS-G-2 exhibits excellent long-term electrochemical stability for 10 h in both the OER and ORR. ZABs assembled for FePNS-G-2 shows a higher power density (168.3 mW cm−2) and a higher specific capacity (782.36 mA h g−1) than benchmark Pt/C + IrO2 electrocatalyst. The sturdy durability of FePNS-G-2 for OER and ORR leads to the charge–discharge cycle durability. The excellent electrocatalytic activity and steady cycling life of FePNS-G-2 examines the air cathode as an electrocatalyst in feasible ZAB applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Chu S, Majumdar A (2012) Opportunities and challenges for a sustainable energy future. Nature 488:294–303

    Article  CAS  PubMed  Google Scholar 

  2. Park D, Ju H, Kim J (2021) Enhanced thermoelectric properties of flexible N-type Ag2Se nanowire/polyvinylidene fluoride composite films synthesized via solution mixing, 93:333–338.

  3. Kim M, Park J, Ju H, Kim JY, Cho H-S, Kim C-H, Kim B-H, Lee SW (2021) Understanding synergistic metal–oxide interactions of in situ exsolved metal nanoparticles on a pyrochlore oxide support for enhanced water splitting. Energ Environ Sci 14:3053–3063

    Article  CAS  Google Scholar 

  4. Wang H-F, Tang C, Zhang Q (2018) A review of precious-metal-free bifunctional oxygen electrocatalysts: rational design and applications in Zn−air batteries. Adv Func Mater 28:1803329

    Article  CAS  Google Scholar 

  5. Pan J, Xu YY, Yang H, Dong Z, Liu H, Xia BY (2018) Advanced architectures and relatives of air electrodes in Zn-air batteries. Adv Sci 5:1700691

    Article  CAS  Google Scholar 

  6. Lee J-S, Tai Kim S, Cao R, Choi N-S, Liu M, Lee KT, Cho J (2011) Metal-air batteries with high energy density: Li-air versus Zn-air. Adv Energy Mater 1:34–50

    Article  CAS  Google Scholar 

  7. Zhang Y, Deng Y-P, Wang J, Jiang Y, Cui G, Shui L, Yu A, Wang X, Chen Z (2021) Recent progress on flexible Zn-air batteries. Energy Storage Mater 35:538–549

    Article  Google Scholar 

  8. Liu Q, Pan Z, Wang E, An L, Sun G (2020) Aqueous metal-air batteries: fundamentals and applications. Energy Storage Mater 27:478–505

    Article  Google Scholar 

  9. He Y, Shang W, Ni M, Huang Y, Zhao H, Tan P (2022) In-situ observation of the gas evolution process on the air electrode of Zn-air batteries during charging. Chem Eng J 427:130862

    Article  CAS  Google Scholar 

  10. Ma Y, Shang W, Yu W, Chen X, Xia W, Wang C, Tan P (2021) Synthesis of ultrasmall NiCo2O4 nanoparticle-decorated N-doped graphene nanosheets as an effective catalyst for Zn–air batteries. Energy Fuels 35:14188–14196

    Article  CAS  Google Scholar 

  11. Tan P, Chen B, Xu H, Cai W, He W, Chen M, Ni M (2019) Synthesis of Fe2O3 Nanoparticle-Decorated N-doped reduced graphene oxide as an effective catalyst for Zn-air batteries. J Electrochem Soc 166:A616–A622

    Article  CAS  Google Scholar 

  12. Kim K, Wie J, Kim J (2020) Synergistic interaction of P and N co-doping EDTA with controllable active EDTA-cobalt sites as efficient electrocatalyst for oxygen reduction reaction. J Ind Eng Chem 83:252–259

    Article  CAS  Google Scholar 

  13. Kim M, Ju H, Kim J (2019) Single crystalline Bi2Ru2O7 pyrochlore oxide nanoparticles as efficient bifunctional oxygen electrocatalyst for hybrid Na-air batteries. Chem Eng J 358:11–19

    Article  CAS  Google Scholar 

  14. Kim M, Ju H, Kim J (2018) Highly efficient bifunctional catalytic activity of bismuth rhodium oxide pyrochlore through tuning the covalent character for rechargeable aqueous Na–air batteries. J Mater Chem A 6:8523–8530

    Article  CAS  Google Scholar 

  15. Lai C, Gong M, Zhou Y, Fang J, Huang L, Deng Z, Liu X, Zhao T, Lin R, Wang K, Jiang K, Xin H, Wang D (2020) Sulphur modulated Ni3FeN supported on N/S co-doped graphene boosts rechargeable/flexible Zn-air battery performance. Appl Catal B 274:119086

    Article  CAS  Google Scholar 

  16. Liang S, Liang C (2019) High-density cobalt nanoparticles encapsulated with nitrogen-doped carbon nanoshells as a bifunctional catalyst for rechargeable zinc-air battery. Mater (Basel) 12:243

    Article  CAS  Google Scholar 

  17. Gu L, Sun X-L, Zhao J, Gong B-Q, Bao Z-L, Jia H-L, Guan M-Y, Ma S-S (2021) A highly efficient bifunctional electrocatalyst (ORR/OER) derived from GO functionalized with carbonyl, hydroxyl and epoxy groups for rechargeable zinc–air batteries, New. J Chem 45:6535–6542

    CAS  Google Scholar 

  18. Masa J, Xia W, Sinev I, Zhao A, Sun Z, Grutzke S, Weide P, Muhler M, Schuhmann W (2014) Mn(x)O(y)/NC and Co(x)O(y)/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes. Angew Chem Int Ed 53:8508–8512

    Article  CAS  Google Scholar 

  19. Fu G, Cui Z, Chen Y, Li Y, Tang Y, Goodenough JB (2017) Ni3Fe-N doped carbon sheets as a bifunctional electrocatalyst for air cathodes. Adv Energy Mater 7:1601172

    Article  CAS  Google Scholar 

  20. Lee DU, Park MG, Park HW, Seo MH, Ismayilov V, Ahmed R, Chen Z (2015) Highly active Co-doped LaMnO 3 perovskite oxide and N-doped carbon nanotube hybrid bi-functional catalyst for rechargeable zinc–air batteries. Electrochem Commun 60:38–41

    Article  CAS  Google Scholar 

  21. Zhang J, Fu J, Song X, Jiang G, Zarrin H, Xu P, Li K, Yu A, Chen Z (2016) Laminated cross-linked nanocellulose/graphene oxide electrolyte for flexible rechargeable zinc-air batteries. Adv Energy Mater 6:1600476

    Article  CAS  Google Scholar 

  22. Wang C, Li Z, Wang L, Niu X, Wang S (2019) Facile synthesis of 3D Fe/N codoped mesoporous graphene as efficient bifunctional oxygen electrocatalysts for rechargeable Zn–air batteries, ACS Sustain. Chem Eng 7:13873–13885

    CAS  Google Scholar 

  23. Jiang H, Yao Y, Zhu Y, Liu Y, Su Y, Yang X, Li C (2015) Iron carbide nanoparticles encapsulated in mesoporous Fe-N-doped graphene-like carbon hybrids as efficient bifunctional oxygen electrocatalysts. ACS Appl Mater Interfaces 7:21511–21520

    Article  CAS  PubMed  Google Scholar 

  24. Ambrosi A, Chua CK, Bonanni A, Pumera M (2014) Electrochemistry of graphene and related materials. Chem Rev 114:7150–7188

    Article  CAS  PubMed  Google Scholar 

  25. Cui W, Cheng N, Liu Q, Ge C, Asiri AM, Sun X (2014) Mo2C nanoparticles decorated graphitic carbon sheets: biopolymer-derived solid-state synthesis and application as an efficient electrocatalyst for hydrogen generation. ACS Catal 4:2658–2661

    Article  CAS  Google Scholar 

  26. Chen WF, Wang CH, Sasaki K, Marinkovic N, Xu W, Muckerman JT, Zhu Y, Adzic RR (2013) Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production, Energy Environ. Sci 6:943–951

    CAS  Google Scholar 

  27. Kim JY, Jang J-W, Youn DH, Magesh G, Lee JS (2014) A stable and efficient hematite photoanode in a neutral electrolyte for solar water splitting: towards stability engineering. Adv Energy Mater 4:1400476

    Article  CAS  Google Scholar 

  28. Zhao R, Chen Y, Huang S (2021) Doping engineering on carbons as electrocatalysts for oxygen reduction reaction. Fundam Res 1:807–823

    Article  CAS  Google Scholar 

  29. Zhang J, Zhang J, He F, Chen Y, Zhu J, Wang D, Mu S, Yang HY (2021) Defect and doping Co-engineered non-metal nanocarbon ORR electrocatalyst. Nanomicro Lett 13:65

    CAS  PubMed  PubMed Central  Google Scholar 

  30. Hu C, Dai L (2019) Doping of carbon materials for metal-free electrocatalysis. Adv Mater 31:1804672

    Article  CAS  Google Scholar 

  31. Yang L, Shui J, Du L, Shao Y, Liu J, Dai L, Hu Z (2019) Carbon-based metal-free ORR electrocatalysts for fuel cells: past, present, and future. Adv Mater 31:1804799

    Article  CAS  Google Scholar 

  32. Paraknowitsch JP, Thomas A (2013) Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications, Energy Environ. Sci 6:2839–2855

    CAS  Google Scholar 

  33. Li JC, Hou PX, Liu C (2017) Heteroatom-doped carbon nanotube and graphene-based electrocatalysts for oxygen reduction reaction. Small 13:1702002

    Article  CAS  Google Scholar 

  34. Zhang J, Dai L (2015) Heteroatom-doped graphitic carbon catalysts for efficient electrocatalysis of oxygen reduction reaction. ACS Catal 5:7244–7253

    Article  CAS  Google Scholar 

  35. Zhang J, Zhao Z, Xia Z, Dai L (2015) A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotechnol 10:444–452

    Article  CAS  PubMed  Google Scholar 

  36. Tian G-L, Zhang Q, Zhang B, Jin Y-G, Huang J-Q, Su DS, Wei F (2014) Toward full exposure of “active sites”: nanocarbon electrocatalyst with surface enriched nitrogen for superior oxygen reduction and evolution reactivity. Adv Funct Mater 24:5956–5961

    Article  CAS  Google Scholar 

  37. Zheng Y, Chen S, Zhang KAI, Zhu J, Xu J, Zhang C, Liu T (2021) Ultrasound-triggered assembly of covalent triazine framework for synthesizing heteroatom-doped carbon nanoflowers boosting metal-free bifunctional electrocatalysis. ACS Appl Mater Interfaces 13:13328–13337

    Article  CAS  PubMed  Google Scholar 

  38. Li P, Wang H, Fan W, Huang M, Shi J, Shi Z, Liu S (2021) Salt assisted fabrication of lignin-derived Fe, N, P, S codoped porous carbon as trifunctional catalyst for Zn-air batteries and water-splitting devices. Chem Eng J 421:129704

    Article  CAS  Google Scholar 

  39. Gao Z, Liu X, Zhang C, Ren Y (2022) Room-temperature seeded growth of tetraphenylphosphonium bromide single-crystalline fibers, cryst. Growth Des 22:2050–2057

    Article  CAS  Google Scholar 

  40. Hu C, Dai L (2017) Multifunctional carbon-based metal-free electrocatalysts for simultaneous oxygen reduction, oxygen evolution, and hydrogen evolution. Adv Mater 29:1604942

    Article  CAS  Google Scholar 

  41. Paudel DR, Pan UN, Singh TI, Gudal CC, Kim NH, Lee JH (2021) Fe and P doped 1T-phase enriched WS23D-dendritic nanostructures for efficient overall water splitting. Appl Catal B 286:119897

    Article  CAS  Google Scholar 

  42. 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 10:2251–2259

    Article  CAS  PubMed  Google Scholar 

  43. Sun J, Lowe SE, Zhang L, Wang Y, Pang K, Wang Y, Zhong Y, Liu P, Zhao K, Tang Z, Zhao H (2018) Ultrathin nitrogen-doped holey carbon@graphene bifunctional electrocatalyst for oxygen reduction and evolution reactions in alkaline and acidic media. Angew Chem Int Ed 57:16511–16515

    Article  CAS  Google Scholar 

  44. Chen Y, Wang H, Liu F, Gai H, Ji S, Linkov V, Wang R (2018) Hydrophobic 3D Fe/N/S doped graphene network as oxygen electrocatalyst to achieve unique performance of zinc-air battery. Chem Eng J 353:472–480

    Article  CAS  Google Scholar 

  45. Chen Y, Huo S, Wang H (2018) Engineering morphology and porosity of N, S-doped carbons by ionothermal carbonisation for increased catalytic activity towards oxygen reduction reaction, Micro. Nano Lett 13:530–535

    CAS  Google Scholar 

  46. Wang L, Ambrosi A, Pumera M (2013) “Metal-free” catalytic oxygen reduction reaction on heteroatom- doped graphene is caused by trace metal impurities. Angew Chem Int Ed Engl 52:13818–13821

    Article  CAS  PubMed  Google Scholar 

  47. Chung MW, Choi CH, Lee SY, Woo SI (2015) Dimensionality-dependent oxygen reduction activity on doped graphene: is graphene a promising substrate for electrocatalysis? Nano Energy 11:526–532

    Article  CAS  Google Scholar 

  48. Pampel J, Fellinger T-P (2016) Opening of bottleneck pores for the improvement of nitrogen doped carbon electrocatalysts. Adv Energy Mater 6:1502389

    Article  CAS  Google Scholar 

  49. Wang B, Xu L, Liu G, Zhang P, Zhu W, Xia J, Li H (2017) Biomass willow catkin-derived Co3O4/N-doped hollow hierarchical porous carbon microtubes as an effective tri-functional electrocatalyst. J Mater Chem A 5:20170–20179

    Article  CAS  Google Scholar 

  50. Gao Z, Liu X, Zhang C, Ren Y (2022) Room-temperature seeded growth of tetraphenylphosphonium bromide single-crystalline fibers. Cryst Growth Des 22:2050–2057

    Article  CAS  Google Scholar 

  51. Zhao J, Liu Y, Quan X, Chen S, Zhao H, Yu H (2016) Nitrogen and sulfur co-doped graphene/carbon nanotube as metal-free electrocatalyst for oxygen evolution reaction: the enhanced performance by sulfur doping. Electrochim Acta 204:169–175

    Article  CAS  Google Scholar 

  52. Liu K, Peng Z, Wang H, Ren Y, Liu D, Li J, Tang Y, Zhang N (2017) Fe3C@Fe/N doped graphene-like carbon sheets as a highly efficient catalyst in al-air batteries. J Electrochem Soc 6(164):475–483

    Article  CAS  Google Scholar 

  53. Wu J, Zheng X, Jin C, Tian J, Yang R (2015) Ternary doping of phosphorus, nitrogen, and sulfur into porous carbon for enhancing electrocatalytic oxygen reduction. Carbon 92:327–338

    Article  CAS  Google Scholar 

  54. Shao D, Li P, Zhang R, Zhao C, Wang D, Zhao C (2019) One-step preparation of Fe-doped Ni3S2/rGO@NF electrode and its superior OER performances. Int J Hydrog Energy 44:2664–2674

    Article  CAS  Google Scholar 

  55. Gokhale R, Tsui L-K, Roach K, Chen Y, Hossen MM, Artyushkova K, Garzon F, Atanassov P (2018) Hydrothermal synthesis of platinum-group-metal-free catalysts: structural elucidation and oxygen reduction catalysis. ChemElectroChem 5:1848–1853

    Article  CAS  Google Scholar 

  56. Wu N, Zhai M, Chen F, Zhang X, Guo R, Hu T, Ma M (2020) Nickel nanocrystal/nitrogen-doped carbon composites as efficient and carbon monoxide-resistant electrocatalysts for methanol oxidation reactions. Nanoscale 12:21687–21694

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This research was supported by the Chung-Ang University Research Scholarship Grants in 2021 and also funded and conducted under the Competency Development Program for Industry Specialists of the Korean Ministry of Trade, Industry and Energy (MOTIE), operated by Korea Institute for Advancement of Technology (KIAT) (No. P0012453, Next-generation Display Expert Training Project for Innovation Process and Equipment, Materials Engineers).

Author information

Authors and Affiliations

  1. School of Chemical Engineering & Materials Science, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul, Korea

    Dukhyun Nam & Jooheon Kim

  2. Department of Advanced Materials Engineering, Chung-Ang University, Anseong-si, Gyeonggi-do, 17546, Republic of Korea

    Jooheon Kim

  3. Department of Intelligent Energy and Industry, Graduate School, Chung-Ang University, Seoul, 06974, Republic of Korea

    Jooheon Kim

Authors
  1. Dukhyun Nam
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jooheon Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jooheon Kim.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 7952 KB)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nam, D., Kim, J. Fe, P, N, S multidoping porous graphene material as a Bifunctional OER/ORR electrocatalytic activity for enhancing rechargeable Zn-air batteries. Ionics 28, 4719–4728 (2022). https://doi.org/10.1007/s11581-022-04702-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-022-04702-4

Keywords

Search

Navigation