Unlocking 5300-h ultrastable metal-free ORR catalysts for Zn-air batteries via F-N co-doped tailored carbon pore architectures and synergistic adsorption modulation

doi:10.1016/S1872-2067(25)64835-2

Abstract

Abstract:

Designing exceptional-performance and long-lasting oxygen reduction reaction (ORR) catalysts is a critical challenge for the development of rechargeable Zn-air batteries (ZABs). In this study, we introduce a metal-free ORR catalyst composed of F-N co-doped hollow carbon (FNC), specifically engineered to address the limitations of conventional catalysts. The FNC catalysts were synthesized using a template-assisted pyrolysis method, resulting in a hollow, porous architecture with a high specific surface area and numerous active sites. Concurrently, F doping optimized the electronic configuration of pyridinic nitrogen. The introduction of C-F bonds reduced the reaction energy barrier, and the resulting N-C-F configuration enhanced the stability of the nitrogen center. The catalyst exhibits outstanding ORR activity in alkaline media, exhibiting a half-wave potential (E_1/2) of 0.87 V, surpassing that of commercial Pt/C (E_1/2 = 0.85 V). When applied to both aqueous and flexible ZAB configurations, the FNC catalyst achieved peak power densities of 172 and 85 mW cm^-2, respectively, along with exceptional cycling stabilities exceeding 5300 and 302 h, respectively. This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs, particularly for use in flexible and wearable microelectronic devices.

Key words: Heteroatom doping, Metal-free carbon, Oxygen reduction reaction, Stability, Zn-air batteries

Baofa Liu, Weijie Pan, Zhiyang Huang, Yi Zhao, Zuyang Luo, Tayirjan Taylor Isimjan, Bao Wang, Xiulin Yang. Unlocking 5300-h ultrastable metal-free ORR catalysts for Zn-air batteries via F-N co-doped tailored carbon pore architectures and synergistic adsorption modulation[J]. Chinese Journal of Catalysis, 2025, 79: 100-111.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64835-2

https://www.cjcatal.com/EN/Y2025/V79/I12/100

Figures/Tables 6

Fig. 1. Preparation of FNC catalyst. (a) Schematic of the preparation of FNC-900. SEM (b) and TEM (c,d) images (inset: SAED image). (e) HAADF-STEM and corresponding elemental mapping images of FNC-900. (f) N2 adsorption-desorption isotherms. (g) Pore size distribution curves. (h) Bubble contact angle images. (i) Raman spectra. (j) TGA curves of SiO2@NC mixed with NH4F in a 1:10 ratio.

Fig. 2. High-resolution C 1s (a), F 1s (b), and N 1s (c) XPS spectra of FNC-800, FNC-900, and FNC-1000. (d) Content of different C?F bonds. (e) Relative contents of different N species. (f) Valance band and secondary electron tail threshold spectra.

Fig. 3. Electrochemical tests of FNC-900 and other reference catalysts. CV curves (a), LSV polarization curves (b), and corresponding Tafel slope plots (c). (d) jk curves of as-prepared catalysts. (e) Comparison of the ORR activities of FNC-900 and recently reported catalysts. (f) LSV curves of FNC-900 at various rotation rates and K-L plots (inset). (g) H2O2 yield (%) and electron transfer number (n). (h) Cdl values of NC, FNC-800, FNC-900, and FNC-1000. (i) Stability test of FNC-900 and 20 wt% Pt/C in 0.1 mol L?1 KOH at a rotating speed of 1600.

Fig. 4. Performance of aqueous ZABs. (a) Schematic of a self-assembled ZAB with flowing electrolyte. (b) OCV plots (annotated inset: multimeter-measured OCV and ZAB-driven LED illumination). (c) Discharge polarization curves and power densities. (d) Discharge curves at various current densities, with each step lasting for 20 min (x indicates different current density values of 2?50 mA cm-2). (e) Performance comparison of an FNC-900 assembled ZAB and recently reported catalysts in literature. (f) Charge-discharge cycle curves at a current density of 5 mA cm-2.

Fig. 5. Performance of solid-state ZABs. (a) OCV of flexible ZABs. Inset: Schematic of a flexible ZAB and an image of the flexible ZAB powering an LED light. (b) Discharging capacity plots at a constant current density under 5 mA cm-2. Inset: an image of a flexible ZAB powering a mini fan. (c) Discharge polarization curves and power densities. (d) Charge-discharge cycle curves at a current density of 1 mA cm-2. Inset: Image of a flexible ZAB lighting up an LED panel at different bending angles. (e) OCV of a button-type all-solid-state ZAB. Insect: Simplified schematic of the button-type all-solid-state ZAB. (f) Image of a coin cell employing FNC-900 powering a mini fan and an LED panel. (g) Power density and (h) cycling stability of coin cells.

Fig. 6. Theoretical and in-situ studies unveil the mechanism of enhanced ORR activity. (a) In-situ Raman spectrum of FNC-900 obtained in the potential range of 0.3-1.0 V (vs. RHE) during the ORR process. (b) In-situ ATR-IRAS spectrum recorded in the potential range of 0.3-1.1 V (vs. RHE) during ORR. (c) Charge density difference between FNC-900 and NC (yellow and cyan areas display the accumulation and depletion of charges, respectively). (d) Gibbs free energy profiles for FNC-pyridinic-N, FNC-pyrrolic-N, and NC-pyridinic-N. (e) DOS plots for FNC and NC. (f) COHP analysis of N active sites and O atoms of *O intermediates.

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