N/P Co-Doped Nanowrinkled Carbon Spheres Enabling Robust Metal-Free Cathodes for High-Performance Zinc-Air Batteries
Source abstract
Abstract
Abstract The pursuit of productive and resilient metal-free electrocatalysts for the oxygen reduction reaction (ORR) is imperative for realizing advanced zinc-air battery (ZAB) technologies. Herein, we report a nanowrinkled nitrogen/phosphorus codoped carbon sphere (CNP) synthesized via an in situ heteroatom incorporation followed by a pyrolysis strategy. The resulting catalyst uniformly distributes N and P dopants, enabling optimized defect density and enhanced electronic modulation. XPS analysis reveals abundant pyridinic (17.96%) and pyrrolic nitrogen (52.97%) species as key active sites, which promote favorable oxygen adsorption and accelerate charge-transfer kinetics. When integrated into a liquid ZAB, the CNP cathode achieves a high peak power density of 202.2 mW cm–2 and a specific capacity of 768.8 mAhgZn−1, and flexible ZABs exhibit a peak power density of 67.5 mW cm–2 with steady output during mechanical deformation. This work reveals that synergistic N/P electronic regulation integrated with nanostructural design provides a viable route toward highly durable and efficient metal-free air cathodes.
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Research context
OpenAlex topics: Advanced battery technologies research · Nanomaterials and Printing Technologies · Corrosion Behavior and Inhibition
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Guangxi Normal University , , ,
Saudi Arabia Basic Industries Corporation (SABIC) at King Abdullah University of Science and Technology (KAUST) , ,
Southern University of Science and Technology , , ,
Funding
Natural Science Foundation of Guangxi Zhuang Autonomous Region · National Natural Science Foundation of China · Guangxi Science and Technology Projects
References (60)
Show source-provided references
1. Modulation in Spin State of Co3O4 Decorated Fe Single Atom Enables a Superior Rechargeable Zinc-Air Battery Performance10.1002/adma.202414801 ↗
2. Freestanding Metal-Organic Frameworks and Their Derivatives: An Emerging Platform for Electrochemical Energy Storage and Conversion10.1021/acs.chemrev.1c00978 ↗
3. Delocalized electron engineering in metal-air batteries: formation mechanisms, regulation strategies, and applications10.1016/j.ccr.2025.217214 ↗
4. Electronic Communication Between Single Atomic Nickel and Iron-Nitrogen Species Promote the Bifunctional Oxygen Evolution and Reduction for Efficient Rechargeable Zinc-Air Battery10.1002/adfm.202424597 ↗
5. Unraveling the Tandem Effect of Nitrogen Configuration Promoting Oxygen Reduction Reaction in Alkaline Seawater10.1002/aenm.202400183 ↗
6. Surface-optimized carbon nanocages with tailorable atomic Fe-N4 sites to boost oxygen reduction in long stable zinc-air battery10.1016/j.ensm.2023.102972 ↗
7. Boosting Oxygen Electrocatalytic Activity of Fe-N-C Catalysts by Phosphorus Incorporation10.1021/jacs.2c12933 ↗
8. Co-based bifunctional OER/ORR electrocatalysts: From nanostructure engineering to catalytic mechanism innovation for cutting-edge research in empowering energy conversion systems10.1016/j.ccr.2025.217393 ↗
9. Constructing Three-Phase Heterojunction with 1D/3D Hierarchical Structure as Efficient Trifunctional Electrocatalyst in Alkaline Seawater10.1002/adfm.202205767 ↗
10. Atomically Dispersed Fe-N4 Bridged with MoOx Clusters as a Bifunctional Electrocatalyst for Rechargeable Zn-Air Battery10.1002/adfm.202416215 ↗
11. Oxygen Reduction Reaction in Alkaline Media Causes Iron Leaching from Fe-N-C Electrocatalysts10.1021/jacs.2c02088 ↗
12. Concurrently Boosting Activity and Stability of Oxygen Reduction Reaction Catalysts via Judiciously Crafting Fe–Mn Dual Atoms for Fuel Cells10.1007/s40820-024-01580-5 ↗
13. Operando Fe dissolution in Fe-N-C electrocatalysts during acidic oxygen reduction: impact of local pH change10.1039/D4EE01995D ↗
14. Ligand effects enhancing low-temperature oxygen reduction kinetics in neutral conditions10.1039/D5EE01407G ↗
15. Electronic structure regulation of noble metal-free materials toward alkaline oxygen electrocatalysis10.1016/j.esci.2023.100141 ↗
16. Beyond the N-doping controversy: Molecularly deciphering the active origins in metal-free carbon for electrocatalytic oxygen reduction reaction10.1016/j.jechem.2025.08.006 ↗
17. Oxygen Reduction Reaction on Pyridinic Nitrogen-Functionalized Carbon: Active Site Quantification and Effects of Lewis Basicity10.1021/acscatal.4c05289 ↗
18. 3-component (N, Fe, Co). atomically dispersed ORR catalysts prepared by laser-driven decomposition of organic precursors10.1016/j.cej.2025.171198 ↗
19. Untangling the respective effects of heteroatom-doped carbon materials in batteries, supercapacitors and the ORR to design high performance materials10.1039/D1EE00166C ↗
20. B co-doped carbon nanotubes as efficient metal-free electrocatalysts for ORR and Zn-air batteries10.1016/j.cej.2021.130134 ↗
21. A Fullerene Seeded Strategy for Facile Construction of Nitrogen-Doped Carbon Nano-Onions as Robust Electrocatalysts10.1002/adfm.202302100 ↗
22. Phosphorus/Sulfur-Modulated p-Band Center of Pentagonal Carbon for Efficient Oxygen Reduction Reaction10.1021/jacs.5c11300 ↗
23. N-P covalent bond regulation of mesoporous carbon-based catalyst for lowered oxygen reduction overpotential and enhanced zinc-air battery performance10.1016/j.jcis.2024.05.221 ↗
24. Engineering electronic transfer dynamics and ion adsorption capability in dual-doped carbon for high-energy potassium ion hybrid capacitors10.1021/acsnano.2c00140 ↗
25. Constructing Asymmetrical Coordination Microenvironment with Phosphorus-Incorporated Nitrogen-Doped Carbon to Boost Bifunctional Oxygen Electrocatalytic Activity10.1002/adfm.202314444 ↗
26. Elucidating surface redox charge storage of phosphorus-incorporated graphenes with hierarchical architectures10.1016/j.nanoen.2015.05.010 ↗
27. Electrocatalytic Oxygen Reduction Using Metastable Zirconium Suboxide10.1002/anie.202404374 ↗
28. Dual-phase Co/CoFe nanoparticles anchored on N, F co-doped hollow carbon microcapsules as efficient bifunctional catalysts for aqueous/quasi-solid-state Zn-air batteries10.1016/j.cej.2026.175339 ↗
29. A Universal Method for Regulating Carbon Microcrystalline Structure for High-Capacity Sodium Storage: Binding Energy As Descriptor10.1021/acsnano.3c08889 ↗
30. N, F-Codoped Microporous Carbon Nanofibers as Efficient Metal-Free Electrocatalysts for ORR10.1007/s40820-019-0240-x ↗
31. Synergistic Phosphorus Modification of Iron-Nitrogen-Carbon Electrocatalysts for Durable Rechargeable Zinc-air Batteries10.31635/ccschem.025.202505785 ↗
32. Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium10.1002/anie.201006768 ↗
33. Multiscale engineering of N-CoP@NC/3D-NC bifunctional electrocatalyst: Synergistic interface and doping design for high-performance zinc-air batteries10.1002/smll.202513939 ↗
34. Two-Dimensional Phosphorus-Doped Carbon Nanosheets with Tunable Porosity for Oxygen Reactions in Zinc-air Batteries10.1021/acscatal.7b02739 ↗
35. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis10.1021/nn103584t ↗
36. P and S active sites on hierarchical porous carbon nanoshells for superior oxygen reduction reaction and rechargeable Zn-air batteries10.1016/j.jcis.2022.11.144 ↗
37. “One-stone, Two-birds”: Zinc-rich metal-organic frameworks as precursors for high-entropy Zn-air battery electrocatalysts with hierarchical pore structures10.1002/anie.202413826 ↗
38. Biomass-derived phosphorus-doped nanocarbon: A metal-free electrode for high-performance supercapacitors10.1016/j.est.2025.117586 ↗
39. Tailoring the d-band center of iridium-doped cobalt selenide for dual-boosted hydrogen and oxygen evolution reactions10.1016/j.nanoms.2024.01.011 ↗
40. and S tri-doped holey carbon as an efficient electrocatalyst for oxygen reduction in whole pH range for fuel cell and zinc-air batteries10.1016/j.carbon.2021.04.039 ↗
41. Uleashing efficient and CO-resilient alkaline hydrogen oxidation of Pd3P through phosphorus vacancy defect engineering10.1016/S1872-2067(23)64570-X ↗
42. Two-Dimensional Wrinkled N-Rich Carbon Nanosheets Fabricated from Chitin via Fast Pyrolysis as Optimized Electrocatalyst10.1021/acssuschemeng.0c03104 ↗
43. Engineering Proton-Coupled Electron Transfer to Break Activity-Stability Trade-Off of Oxygen Electroreduction Catalysts for Temperature-Adaptive Zn–Air Battery10.1002/anie.202502019 ↗
44. Fabrication of Nitrogen-Doped Holey Graphene Hollow Microspheres and Their Use as an Active Electrode Material for Lithium Ion Batteries10.1021/am5050604 ↗
45. Synergistic pyridinic-N/pyrrolic-N coordination tailors cobalt electronic states for high-efficiency oxygen reduction in Zn-air batteries10.1039/D5TA05299H ↗
46. Activating the Mn Single Atomic Center for an Efficient Actual Active Site of the Oxygen Reduction Reaction by Spin-State Regulation10.1021/jacs.4c13137 ↗
47. Aligned d-orbital energy level of dual-atom sites catalysts for oxygen reduction reaction in anion exchange membrane fuel cells10.1038/s41467-025-63322-4 ↗
48. One-Minute Synthesis via Electroless Reduction of Amorphous Phosphorus-Doped Graphene for Oxygen Reduction Reaction10.1021/acsaem.1c01075 ↗
49. Surface-enriched ultrafine Pt nanoparticles coupled with defective CoP as efficient trifunctional electrocatalyst for overall water splitting and flexible Zn-air battery10.1016/S1872-2067(22)64198-6 ↗
50. A “Pre-Division Metal Clusters” Strategy to Mediate Efficient Dual-Active Sites ORR Catalyst for Ultralong Rechargeable Zn-Air Battery10.1002/anie.202216950 ↗
51. Design of highly active and durable oxygen evolution catalyst with intrinsic chlorine inhibition property for seawater electrolysis10.1016/j.nanoms.2023.10.003 ↗
52. Two-dimensional CoS/Co-MOF Composite Electrocatalyst for Efficient Oxygen Evolution Reaction10.26599/ECS.2025.9600052 ↗
53. A “Dual Spatial Confinement” Route to Tailor Efficient Dual-Active Sites ORR Catalyst for Rechargeable Zn-Air Batteries10.1002/smll.202504022 ↗
54. Unlocking 5300-h ultrastable metal-free ORR catalysts for Zn-air batteries via F–N co-doped tailored carbon pore architectures and synergistic adsorption modulation10.1016/S1872-2067(25)64835-2 ↗
55. Enhanced oxygen reduction reaction performance in boron carbon nitride through P doping for zinc-air batteries10.1016/j.apsusc.2025.163913 ↗
56. Construction of imide-linked covalent organic frameworks with palladium nanoparticles for oxygen reduction reaction10.1002/ece2.32 ↗
57. Advances and challenges of methanol-tolerant oxygen reduction reaction electrocatalysts for the direct methanol fuel cell10.1016/j.jechem.2022.11.023 ↗
58. Hierarchical mesoporous N-doped carbon as an efficient ORR/OER bifunctional electrocatalyst for rechargeable zinc–air battery10.1039/D4QI00637B ↗
59. Coupling of metallic Co with atomic Co–N–C as efficient bifunctional oxygen electrocatalyst for rechargeable zinc-air battery10.1016/j.jallcom.2025.184447 ↗
60. Fe-MOF-Derived Efficient ORR/OER Bifunctional Electrocatalyst for Rechargeable Zinc–Air Batteries10.1021/acsami.0c11945 ↗