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

doi:10.6023/A20090428

摘要/Abstract

针对水系锌离子电池锰基正极材料存在比容量低、循环稳定性差等问题, 本工作利用水热法制备出棒状结构的α-MnO₂, 通过柠檬酸钠高温碳化制备多孔碳, 进而通过超声分散等处理制备出α-MnO₂/PCSs复合材料. 三维的多孔网络有助于提高电子导电性, 提供一个稳定的支撑;α-MnO₂纳米棒均匀地附着在多孔碳纳米片层表面, 有效地避免α-MnO₂的团聚, 从而提高锌离子传输效率. 得益于α-MnO₂/PCSs独特的结构优势, 将其作为锌离子电池正极材料, 在电流密度为0.1 A•g^–1的条件下循环100次后, 其可逆容量为350 mAh•g^–1, 在1 A•g^–1的大的电流密度下, 经过1000圈循环后, 容量可达160 mAh•g^–1, 展现了优异的循环稳定性能, 有望成为高性能锌离子电池的潜在正极材料.

关键词: 水系锌离子电池, 正极材料, α-MnO2纳米棒, 多孔碳纳米片, 电化学性能

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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李燕丽, 于丹丹, 林森, 孙东飞, 雷自强. 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[J]. 化学学报, 2021, 79(2): 200-207.

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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图/表 6

图1. (a) α-MnO 2纳米棒和α-MnO2/PCSs复合材料的XRD衍射图谱. 插图: α-MnO 2的晶体结构. (b) α-MnO 2/PCSs复合材料的拉曼图谱. (c) α-MnO 2纳米棒和α-MnO2/PCSs复合材料的N2-吸/脱附曲线图. (d) α-MnO 2纳米棒和α-MnO2/PCSs复合材料的孔结构分布曲线图

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

图2. (a) α-MnO 2的SEM. 插图: α-MnO 2的HRTEM. (b), (c) 分别为PCSs和α-MnO2/PCSs复合材料的SEM. (d) α-MnO 2/PCSs复合材料的HRSEM. (e, f) α-MnO 2/PCSs复合材料的TEM. 插图: α-MnO 2/PCSs复合材料的HRTEM

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

图3. α-MnO2/PCSs复合材料的XPS图谱. (a) 全谱. (b) C1s的精细图谱. (c) O1s的精细图谱. (d) Mn2p的精细图谱

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

图4. (a) α-MnO 2/PCSs复合材料的前三圈的CV曲线. (b) α-MnO 2和α-MnO2/PCSs复合材料的CV曲线. (c) α-MnO 2/PCSs复合材料的前三圈充放电曲线图. (d) α-MnO 2和α-MnO2/PCSs复合材料的循环性能图. (e) α-MnO 2和α-MnO2/PCSs复合材料的倍率性能图. (f) α-MnO 2/PCSs复合材料的长循环性能和库伦效率图

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

图5. 对α-MnO2/PCSs电极的Zn2+的电化学行为的动力学分析. (a) 不同电流密度(0.1 mV•s–1到1.0 mV•s–1)的CV曲线. (b) 通过峰电流和扫描速率之间的关系来确定b值曲线. (c) α-MnO 2和α-MnO2/PCSs复合材料的阻抗图. (d, e) 对α-MnO2和α-MnO2/PCSs复合材料的离子扩散系数进行了GITT测试并进行了相应的分析

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

图6. α-MnO2/PCSs复合材料的制备示意图

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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