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. 2023 Jun 9;13(25):17370-17383.
doi: 10.1039/d3ra02802j. eCollection 2023 Jun 5.

Influence of ZIF-9 and ZIF-12 structure on the formation of a series of new Co/N-doped porous carbon composites as anode electrodes for high-performance lithium-ion batteries

Anh T A Duong  1 , Hoang V Nguyen  2   3 , Man V Tran  2   3 , Quynh N Ngo  1 , Loc C Luu  4 , Tan L H Doan  5   6 , Hung N Nguyen  1 , My V Nguyen  1
Affiliations

Influence of ZIF-9 and ZIF-12 structure on the formation of a series of new Co/N-doped porous carbon composites as anode electrodes for high-performance lithium-ion batteries

Anh T A Duong et al. RSC Adv. .

Abstract

A series of new Co/N-doped porous carbon composites, denoted as Co/CZIF-9 and Co/CZIF-12, containing Co nanoparticles encapsulated in nitrogen-doped carbon matrices were prepared by annealing Co-based zeolite imidazolate framework materials, ZIF-9 and ZIF-12, as the efficient precursors at different temperatures. The structural features of the as-synthesized composites at 900 °C were determined by analytical methods with high reliability. Consequently, Co/CZIF-12_900 exhibits a high first specific discharge capacity of 971.0 mA h g-1 at a current density of 0.1 A g-1. Notably, the specific discharge/charge capacity of Co/CZIF-12_900 reaches about 508.8 mA h g-1 at 0.1 A g-1 after 100 cycles. The outstanding behaviors can be accounted for by the efficient incorporation of hetero-nitrogen doping and the Co nanoparticles within the layered structure of porous carbon, enhancing electrical conductivity and structural stability and limiting volume change during the intercalation/deintercalation of Li+ ions. These findings suggest that the Co/CZIF-12_900 material could be employed as a promising anode electrode for energy storage products.

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Conflict of interest statement

The authors maintain that they have no conflict of interest for this communication.

Figures

Fig. 1
Fig. 1. The structure of ZIF-9 and ZIF-12 backbone is constructed from the Co tetrahedral and benzimidazole linkers, indicating the different topologies and the SEM images of Co/N-doped porous carbon, denoted as Co/CZIF-9 and Co/CZIF-12 derived from the ZIF-9 and ZIF-12 precursors. The architectures of ZIF-9 and ZIF-12 are depicted from the cif information with the CCDC numbers 1036076 and 602546, respectively. Atom colors: Co, pink polyhedra; C, black; N, blue. All H atoms are omitted for clarity.
Fig. 2
Fig. 2. PXRD patterns of the pristine ZIF-9 (black), pristine ZIF-12 (red), Co/CZIF-9_900 (blue), and Co/CZIF-12_900 (green) in comparison with Co nanoparticles (purple) (a); PXRD analyses of Co/CZIF-9_600 (black), Co/CZIF-9_700 (red), Co/CZIF-9_800 (blue), and Co/CZIF-9_900 (green) samples (b); PXRD patterns of Co/CZIF-12_600 (black), Co/CZIF-12_700 (red), Co/CZIF-12_800 (blue), and Co/CZIF-12_900 (green) samples (c); Raman spectra of the activated ZIF-9 (red), activated ZIF-12 (blue), Co/CZIF-9_900 (green), and Co/CZIF-12_900 (purple) as compared to the benzimidazole linker (black) (d); Raman spectra of the Co/CZIF-9_700 (black), Co/CZIF-9_800 (red), and Co/CZIF-9_900 (blue) (e); Raman spectra of the Co/CZIF-12_700 (green), Co/CZIF-12_800 (purple), and Co/CZIF-12_900 (dark blue) (f).
Fig. 3
Fig. 3. TGA-DSC curve of the activated ZIF-9 material under an N2 atmosphere (a); TGA-DSC diagram of the activated ZIF-12 sample under an N2 medium (b); N2 adsorption–desorption isotherm and pore size distribution of Co/CZIF-9_900 (c); N2 adsorption–desorption isotherm and pore size distribution of Co/CZIF-12_900 (d).
Fig. 4
Fig. 4. XPS spectra of the Co/CZIF-9_900 and Co/CZIF-12_900: the survey of Co/CZIF-9_900 (a); C 1s of Co/CZIF-9_900 (b); N 1s of Co/CZIF-9_900 (c); Co 2p of Co/CZIF-9_900 (d); the survey of Co/CZIF-12_900 (e); C 1s of Co/CZIF-12_900 (f); N 1s of Co/CZIF-12_900 (g); Co 2p of Co/CZIF-12_900 (h).
Fig. 5
Fig. 5. SEM images of the ZIF-9 material (a and b); ZIF-12 material (c and d); Co/CZIF-9_900 composite annealed at 900 °C (e and f); and Co/CZIF-12_900 composite calcined at 900 °C (g and h).
Fig. 6
Fig. 6. Elemental mapping images of Co/CZIF-9_900 composites (a); EDS analysis of Co/CZIF-9_900 composite (b); elemental mapping images of Co/CZIF-12_900 composites (c); EDS analysis of Co/CZIF-12_900 composite (d).
Fig. 7
Fig. 7. The first three CV curves of Co/CZIF-9_900 at 0.1 mV s−1 in the potential range of 0.01–3.0 V (a); the discharge/charge curves of Co/CZIF-9_900 at a current density of 0.1 A g−1 for the first three cycles (b); the first three CV curves of Co/CZIF-12_900 at 0.1 mV s−1 in the potential range of 0.01–3.0 V (c); the discharge/charge curves of Co/CZIF-12_900 at a current density of 0.1 A g−1 for the first three cycles (d).
Fig. 8
Fig. 8. The long-term cycling properties of Co/CZIF-9_900 (a) and Co/CZIF-12_900 (b) at 0.1 A g−1; the rate performance of Co/CZIF-9_900 and Co/CZIF-12_900 at 0.1C to 5C (c) [1C = 1 A g−1]; the Nyquist plots of Co/CZIF-9_900 (d) and Co/CZIF-12_900 (e).
See this image and copyright information in PMC

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