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用于可充电水性锌离子电池的Ti3C2@ε-MnO2电极

黄兰香 罗旭峰

黄兰香, 罗旭峰. 用于可充电水性锌离子电池的Ti3C2@ε-MnO2电极[J]. 复合材料学报, 2022, 39(10): 4631-4641. doi: 10.13801/j.cnki.fhclxb.20211123.002
引用本文: 黄兰香, 罗旭峰. 用于可充电水性锌离子电池的Ti3C2@ε-MnO2电极[J]. 复合材料学报, 2022, 39(10): 4631-4641. doi: 10.13801/j.cnki.fhclxb.20211123.002
HUANG Lanxiang, LUO Xufeng. Advanced Ti3C2@ε-MnO2 cathode as rechargeable aqueous zinc-ion batteries[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 4631-4641. doi: 10.13801/j.cnki.fhclxb.20211123.002
Citation: HUANG Lanxiang, LUO Xufeng. Advanced Ti3C2@ε-MnO2 cathode as rechargeable aqueous zinc-ion batteries[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 4631-4641. doi: 10.13801/j.cnki.fhclxb.20211123.002

用于可充电水性锌离子电池的Ti3C2@ε-MnO2电极

doi: 10.13801/j.cnki.fhclxb.20211123.002
基金项目: 乐山师范学院高层次人才引进科研启动项目(205190161);乐山市科技局重点项目(20GZD031)
详细信息
    通讯作者:

    黄兰香,博士,讲师,研究方向为新能源材料与器件 E-mail: 120678486@qq.com

  • 中图分类号: TB34

Advanced Ti3C2@ε-MnO2 cathode as rechargeable aqueous zinc-ion batteries

  • 摘要: 可充电水性锌-氧化锰(Zn-MnOx)电池具有成本低、安全性高、易于安装等特点,成为太阳能及风能储能装置的最佳选择。由于MnOx导电性欠佳,导致电池循环性能较差,为解决此问题,本文采用导电性优异、具有丰富化学终端(Tx,如=O、—F、—OH)的二维层状过渡金属碳化物(MXene) Ti3C2Tx材料作为MnOx颗粒的良好载体。基于化学终端的电负性,Mn2+能够与其产生强静电吸引,从而嵌入Ti3C2Tx MXene材料层间并吸附在其表面,使生成的Mn3O4颗粒牢牢地锚定在Ti3C2Tx MXene上,形成了Ti3C2@Mn3O4复合材料。当作为水性锌离子电池的正极材料时,Ti3C2@Mn3O4在第1次充电过程中,完全转化为Ti3C2@ε-MnO2。由于Ti3C2Tx MXene材料优异的导电性及层状结构,使Ti3C2@ε-MnO2电极展现出了优异的动力学和电化学性能,在0.2 C (1 C=308 mA·h·g−1)倍率下放电时,比容量高达440 mA·h·g−1,能量密度为607 W·h·kg−1,在1 C倍率下循环150次后,容量从270 mA·h·g−1增长至480 mA·h·g−1。优异的电池性能,简单的材料制备方法再加上低成本、高安全性及易于组装的特性,使可充电水性Zn-MnOx电池在大规模储能装置上的应用成为可能。

     

  • 图  1  Ti3AlC2、Ti3C2Tx MXene、Mn3O4、Ti3C2@Mn3O4的XRD图谱 ((a), (b));Ti3C2@Mn3O4 (c)和Mn3O4 (d) 的Brunner-Emmet-Teller曲线;Ti3C2@Mn3O4中Ti2p (e)、C1s (f)、Mn3s (g)、O1s (h) 的XPS图谱

    Figure  1.  XRD patterns of Ti3AlC2, Ti3C2Tx MXene, Mn3O4, Ti3C2@Mn3O4 ((a), (b)); Brunner-Emmet-Teller curves of Ti3C2@Mn3O4 (c) and Mn3O4 (d); XPS patterns of Ti2p (e), C1s (f), Mn3s (g) and O1s (h) in Ti3C2@Mn3O4

    图  2  Ti3AlC2 MAX (a)、Ti3C2Tx MXene (b) 的SEM图像;Ti3C2@Mn3O4的TEM ((c)~(e)) 和 HRTEM图像(f);Mn、O、Ti和C的EDS图谱 (g)

    Figure  2.  SEM images of Ti3AlC2 MAX (a), Ti3C2Tx MXene (b); TEM images ((c)-(e)) and HRTEM image (f) of Ti3C2@Mn3O4; Corresponding elemental mappings of Mn, O, Ti and C (g)

    图  3  Ti3C2@Mn3O4的电化学性能:(a) 0.2 C (1 C=308 mA·h·g−1)倍率下的充放电曲线;(b) 0.1 mV·s−1扫速下的循环伏安(CV)曲线;((c), (d)) 倍率性能及不同倍率下的充放电曲线;((e), (f)) 1 C倍率下的循环性能及不同循环次数的充放电曲线

    Figure  3.  Electrochemical performance of Ti3C2@Mn3O4: (a) Galvanostatic discharge/charge curves at 0.2 C; (b) Cyclic voltammetry curves at 0.1 mV·s−1; ((c), (d)) Rate performance and corresponding charge/discharge curves at different ratios; ((e), (f)) Cycling performance at 1 C and corresponding charge/discharge curves at different cycles

    图  4  Ti3C2@Mn3O4电极经过不同循环次数后的XRD图谱 (a);Ti3C2@Mn3O4电极充电至1.9 V的SEM微观形貌图:(b) 在0.2 C倍率下经过第1次充电后;(c) 在0.2 C倍率下循环20次后再在1 C倍率下循环3次;(d) 继续在1 C倍率下循环150次

    Figure  4.  XRD patterns of Ti3C2@Mn3O4 cathode after different cycles (a) ; SEM images of Ti3C2@Mn3O4 cathode recharged to 1.9 V: (b) After 1st charge at 0.2 C; (c) After 20 cycles at 0.2 C and 3 cycles at 1 C; (d) 150 cycles at 1 C

    SUS—Steel use stainless

    图  5  (a) Ti3C2@Mn3O4电极在不同扫速下的CV曲线;(b)不同峰位lgi和lgυ的拟合曲线;(c) Ti3C2@Mn3O4和Mn3O4电极的恒流间歇滴定(GITT)曲线及相应的离子扩散系数D

    Figure  5.  (a) CV curves of Ti3C2@Mn3O4 cathode at different scan rates; (b) lgi and lgυ plots at specific peak currents; (c) Galvanostatic intermittent titration technique curves and the corresponding ion diffusion coefficients D of Ti3C2@Mn3O4 and Mn3O4 cathode

    b—Slope of the fitted curve

    图  6  (a) Ti3C2@Mn3O4电极在0.2 C倍率下循环20次后放电至0.8 V的XRD图谱;(b) Ti3C2@Mn3O4电极在0.2 C倍率下循环20次后完全放电至0.8 V和充电至1.9 V的Mn2p XPS图谱

    Figure  6.  (a) XRD pattern of Ti3C2@Mn3O4 cathode after fully discharged to 0.8 V at 0.2 C after 20 cycles; (b) XPS spectrums of Mn2p for Ti3C2@Mn3O4 cathode fully discharged to 0.8 V and recharged to 1.9 V after 20 cycles at 0.2 C

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出版历程
  • 收稿日期:  2021-09-17
  • 修回日期:  2021-11-06
  • 录用日期:  2021-11-13
  • 网络出版日期:  2021-11-24
  • 刊出日期:  2022-08-22

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