大尺寸MXene的制备及柔性透明锌离子混合超级电容器应用

doi:10.6023/A24120385

摘要/Abstract

柔性透明锌离子混合超级电容器(Zinc-ion hybrid supercapacitors, ZHSCs)不仅兼具高能量密度和大功率密度的优势, 还展现出优秀的透光性, 正引领柔性电子技术的新革命. 过渡金属碳/氮化物(MXenes)具有高导电性、大比表面积等特点, 是制备ZHSCs的理想电极材料. 然而, 目前MXenes不仅面临合成片层尺寸小、电化学性能受限的问题, 还面临着合成产率低、成本高、难以大规模应用等问题. 本工作开发了一种简单有效的合成方法, 通过原位刻蚀制得多层Ti₃C₂T_x (MXene), 结合机械振荡法, 用于大尺寸Ti₃C₂T_x的高产率制备. 当剥离时间为1.5 h时, Ti₃C₂T_x薄片尺寸可达5.2 μm, 且有着32.4%的高产率. 采用Ti₃C₂T_x薄膜电极作为正极, 氧化铟锡/聚对苯二甲酸乙二醇酯(ITO/PET)基底电沉积锌作为负极, 以三氟甲烷磺酸锌为电解质, 组装了ZHSCs. 实验结果表明, ZHSCs的电压窗口达到1.2 V, 具有大的面积比电容(7.79 mF•cm^-2)、高功率密度(60.0 µW•cm^-2)、高能量密度(1.56 µWh•cm^-2)和良好的透光度(62.1%), 将其进行180°的弯曲折叠后, 仍有94.1%的电容保留率.

关键词: 锌离子混合超级电容器, 柔性透明电极, MXene纳米片, 大尺寸, 机械振荡

The iteration of intelligent electronic products has promoted the rapid development of flexible transparent electronics, greatly stimulating the demand of matched energy storage units. Flexible transparent zinc-ion hybrid supercapacitors (ZHSCs) not only combine the advantages of high energy density and high power density, but also exhibit excellent transparency, leading a new revolution in flexible electronic technology. Transparent conductive electrode is the most critical component of ZHSCs, which determines the energy storage characteristics of the whole device. Therefore, it is very important to develop advanced electrode materials with high specific capacitance and high optical transmittance. Transition metal carbides/nitrides (MXenes) are considered ideal materials for fabricating ZHSCs due to their high electrical conductivity and large specific surface area. However, it still faces challenges of small flake size and limited electrochemical performance, as well as low synthesis yield, high cost, and difficulty in large-scale application. To address these issues, this work reports a simple and effective method to fabricate high-yield large-sized Ti₃C₂T_x, through in-situ etching approach to prepare multilayer Ti₃C₂T_x (MXene) and mechanical shaking strategy. Using Ti₃C₂T_x electrode as the positive electrode, zinc electro-deposited indium tin oxide/polyethylene terephthalate (ITO/PET) as the negative electrode, and zinc trifluoromethanesulfonate as the electrolyte, an asymmetric ZHSC device was assembled. Experimental results show that when the shaking time is 1.5 h, the Ti₃C₂T_x flake size reaches 5.2 μm with a high yield of 32.4%. The resulting ZHSCs exhibit a voltage window of 1.2 V, a large areal capacitance of 7.79 mF•cm^-2, high power density of 60.0 µW•cm^-2, high energy density of 1.56 µWh•cm^-2, and high transparency of 62.1%. After bending and folding at 180°, the device retains 94.1% of its capacitance. Moreover, the ZHSC-30 device maintains a capacitance retention rate of 82.3% after 1000 cycles at a current density of 600 µA•cm^-2, demonstrating its stable cycling performance. This work provides a powerful method for the fabrication of large-sized MXenes for application in flexible transparent ZHSCs.

Key words: zinc-ion hybrid supercapacitors, flexible transparent electrode, MXene nanosheet, large-size, mechanical shaking

引用此文

方雨田, 白启佳, 王帅康, 万守昊, 高翔, 申一航, 刘瑞卿, 赵翠娥. 大尺寸MXene的制备及柔性透明锌离子混合超级电容器应用[J]. 化学学报, 2025, 83(5): 463-470.

Yutian Fang, Qijia Bai, Shuaikang Wang, Shouhao Wan, Xiang Gao, Yihang Shen, Ruiqing Liu, Cui-e Zhao. Preparation of Large-size MXene and Application in Flexible Transparent Zinc-ion Hybrid Supercapacitors[J]. Acta Chimica Sinica, 2025, 83(5): 463-470.

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图/表 6

图1. 机械振荡法制备二维Ti3C2Tx片层材料的示意图

Figure 1. Schematic diagram of the preparation of two-dimensional Ti3C2Tx nanosheets via the mechanical shaking

图2. 不同剥离时间下Ti3C2Tx的(a) XRD图谱, (b)小角衍射XRD图谱, (c) Raman光谱, (d) FT-IR光谱, (e) UV-vis吸收光谱和(f)产率图

Figure 2. (a) XRD patterns, (b) XRD patterns of small angle diffraction, (c) Raman spectra, (d) FT-IR spectra, (e) UV-vis absorbance spectra and (f) yields of Ti3C2Tx at different exfoliated times

图3. 机械振荡不同时间下剥离的Ti3C2Tx薄片的AFM图: (a) 0.5 h, (b) 1.0 h, (c) 1.5 h, (d) 2.0 h, (e) 2.5 h和(f)超声法制备的Ti3C2Tx

Figure 3. AFM images of Ti3C2Tx sheets at different exfoliated times via the mechanical shaking: (a) 0.5 h, (b) 1.0 h, (c) 1.5 h, (d) 2.0 h, (e) 2.5 h, and (f) S-Ti3C2Tx

图4. 不同浓度下Ti3C2Tx电极的(a)透光率对比图(插图为实物数码照片); (b)扫描速率为100 mV•s-1时的CV曲线; (c)电流密度为50 μA•cm-2时的GCD曲线; (d)方阻图. Ti3C2Tx-1.5电极的(e)不同扫描速率下的CV曲线和(f)不同电流密度下的GCD曲线

Figure 4. Comparisons of different Ti3C2Tx electrodes: (a) optical transmittances (insets are digital photographs); (b) CV curves with a scan rate of 100 mV•s-1; (c) GCD curves with a current density of 50 μA•cm-2; (d) Square resistance plots. Ti3C2Tx-1.5 electrode: (e) CV curves at different scan rates; (f) GCD curves at different current densities

图5. 三明治结构Ti3C2Tx对称器件的电化学性能: (a) CV曲线; (b) GCD曲线; (c) EIS图谱; (d) 不同弯曲角度的CV曲线(扫描速率150 mV•s-1); (e) 不同弯曲角度的GCD曲线(电流密度75 µA•cm-2); (f) 由GCD曲线计算出的不同弯曲角度下的电容保持率; (g)器件的循环稳定性测试; 单个器件与两个器件串/并联的(h) CV曲线和(i) GCD曲线

Figure 5. Electrochemical performance of sandwich-type symmetric device based on Ti3C2Tx electrodes: (a) CV curves at different scanning rates; (b) GCD curves at different current densities; (c) EIS plots; (d) CV curves under different bending angle (scan rate of 150 mV•s-1); (e) GCD curves under different bending angles (current density of 75 µA•cm-2); (f) Capacitance retention at different bending angles calculated from GCD curves; (g) Cyclic stability testing of devices; (h) CV curves of single device and series/parallel devices; (i) GCD curves of single device and series/parallel device

图6. 非对称混合器件ZHSC-30的电化学性能: (a)不同扫描速率下的CV曲线; (b)不同电流密度下的GCD曲线; (c)在600 µA•cm-2电流密度下的电容保持率(插图: 循环第1次和第1000次的GCD曲线); 在不同弯曲角度下的(d) CV曲线和(e)电容保持率(插图: GCD曲线); (f)不同透明器件的Ragone图

Figure 6. Electrochemical performance of asymmetric ZHSC-30 device: (a) CV curves under different scanning rates; (b) GCD curves at different current densities; (c) Capacitance retention at a current density of 600 µA•cm-2 (inset: GCD curves for 1st and 1000th cycles); (d) CV curves at different bending angles; (e) Capacitance retention (inset: GCD curves); (f) Ragone plots of ZHSC-30 with other reported transparent supercapacitors

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