Preparation of α-MnO2 Nanorods/Porous Carbon Cathode for Aqueous Zinc-ion Batteries

doi:10.6023/A20090428

Abstract

Aqueous zinc-ion batteries (ZIBs) have attracted more attention as large-scale energy storage technology due to their high safety, low cost and environmental benignity. To date, numerous cathodes based on manganese dioxide, vanadium dioxide, and polyanionic compounds have been reported. Among them, Manganese oxides have the advantages of low cost, non-toxicity, abundant materials and high working voltage, have been widely explored as promising cathodes for zinc ion batteries. Among them, MnO₂ cathodes are particularly desirable candidates for commercialization owing to their tunnel structure and affordability. α-MnO₂has (1×1) and (2×2) tunnel structures, and Zn²⁺ can rapidly inserted and deserted in the tunnel. However, the capacity of manganese dioxide is fast decaying with the cycles due to the poor conductivity of MnO₂, which limits its electrochemical performance. Herein, α-MnO₂ nanorods are uniformly distributed on the surface of porous carbon nanosheets network (PCSs) by a simple hydrothermal/dispersion method strategy. In the α-MnO₂/PCSs architecture, the α-MnO₂ nanorods and α-MnO₂/PCSs composite were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), etc. The results testified that α-MnO₂/PCSs nanorods were firmly adhered on the surface of porous carbon nanosheets, which can effectively avoid the stacking of α-MnO₂nanorods, while the high conductive carbon network can improve the electrical conductivity of the composite. The porous network can provide effective electron transfer channels, provide stable hosts for fast Zn²⁺ extraction/insertion, and prevent the α-MnO₂nanorods from stacking each other. Benefiting from the unique porous structure and high conductive network, the α-MnO₂/PCSs hybrid shows high reversibility capacity, good rate performance, and outstanding cycling stability. Specifically, α-MnO₂/PCSs exhibits high reversible capacity of 350 mAh•g^–1 after 100 cycles at 0.1 A•g^–1 and maintains a capacity of 160 mAh•g^–1 at a high rate of 1 A•g^–1 after 1000 cycles, thus making it promising cathode for the high performance ZIBs.

Key words: aqueous zinc ion battery, cathode material, α-MnO2 nanorods, porous carbon nanosheets, electrochemical performance

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Yanli Li, Dandan Yu, Sen Lin, Dongfei Sun, Ziqiang Lei. Preparation of α-MnO₂ Nanorods/Porous Carbon Cathode for Aqueous Zinc-ion Batteries[J]. Acta Chimica Sinica, 2021, 79(2): 200-207.

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Fig. & Tab. 6

Figure 1. (a) XRD patterns of α-MnO 2 nanorods and α-MnO 2/PCSs composites. Inset: the crystal structure of α-MnO 2. (b) Raman spectrum of α-MnO 2/PCSs composites. (c) Nitrogen adsorption/desorption isotherms and (d) pore size distribution curve of α-MnO 2nanorods and α-MnO 2/PCSs composites

Figure 2. (a) Scanning electron microscopy (SEM) image of α-MnO 2. Inset: HRTEM of α-MnO 2. (b), (c) SEM of PCSs and α-MnO 2/PCSs composites respectively. (d) α-MnO 2/PCSs composites. (e, f) TEM images of α-MnO 2/PCSs composites, inset: HRTEM of α-MnO 2/PCSs composites

Figure 3. XPS spectra of α-MnO 2/PCSs composites. (a) full spectrum. High-resolution XPS spectra of (b) C1s, (c) O1s and (d) Mn2p

Figure 4. (a) Cyclic voltammetry curves of α-MnO 2/PCSs composites at a scan rates of 0.1 mV•s–1. (b) Cyclic voltammetry curves of α-MnO 2 and α-MnO 2/PCSs composites. (c) The first three cycles of Charge and discharge curves of α-MnO 2/PCSs composites. (d) Cyclic performance of α-MnO 2 and α-MnO 2/PCSs composites. (e) Rate performance of α-MnO 2and α-MnO 2/PCSs composites. (f) Long-term cycle performance and Coulombic efficiency of α-MnO 2/PCSs composites

Figure 5. Kinetic analysis of the electrochemical behavior of Zn2+ of α-MnO2/PCSs electrode. (a) CV curves at various scan rates from 0.1 mV•s–1 to 1.0 mV•s–1. (b) Determination of the b-value using the relationship between peak current and scan rate. (c) Nyquist plot of α-MnO2 and α-MnO2/PCSs composites. (d, e) Calculate the ion diffusion coefficient of α-MnO2 and α-MnO2/PCSs composite materials GITT test was performed and corresponding analysis was performed

Figure 6. Schematic illustration for the synthesis of α-MnO 2/PCSs composite

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α-MnO₂纳米棒/多孔碳正极材料的制备及水系锌离子电池性能研究

Preparation of α-MnO₂ Nanorods/Porous Carbon Cathode for Aqueous Zinc-ion Batteries

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α-MnO2纳米棒/多孔碳正极材料的制备及水系锌离子电池性能研究