用于可充电水性锌离子电池的Ti3C2@ε-MnO2电极

黄兰香; 罗旭峰

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

黄兰香^{1, 2, ,},
罗旭峰^{1, 2}

1.
乐山师范学院　电子与材料工程学院，乐山 614000
2.
西部硅材料光伏新能源产业技术研究院，乐山 614000

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
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出版历程
- 收稿日期: 2021-09-16
- 修回日期: 2021-11-05
- 录用日期: 2021-11-12
- 网络出版日期: 2021-11-23
- 刊出日期: 2022-08-21

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

HUANG Lanxiang^{1, 2, ,},
LUO Xufeng^{1, 2}

1.
Institute of Electronics and Materials Engineering, Leshan Normal University, Leshan 614000, China
2.
West Silicon Materials Photovoltaic and New Energy Industry Technology Research Institute, Leshan 614000, China

摘要

摘要: 可充电水性锌-氧化锰(Zn-MnO_x)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MnO_x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(T_x，如=O、—F、—OH)的二维层状过渡金属碳化物(MXene) Ti₃C₂T_x材料作为MnO_x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Ti₃C₂T_x 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Ti₃C₂T_x 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Ti₃C₂T_x 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-MnO_x电池在大规模储能装置上的应用成为可能。
- 可充电水性锌离子电池 /
- Mn₃O₄ /
- Ti₃C₂T_x MXene /
- Ti₃C₂@ε-MnO₂电极 /
- 可充电电池
Abstract: Due to the low cost, high safety and easy assembly, rechargeable aqueous zinc-manganese oxide (Zn-MnO_x) batteries are the best devices for energy storage. However, poor conductivity of MnO_x results in the bad cycle performance. Herein, highly conductive and layered Ti₃C₂T_x MXene with rich terminations (T_x, for example, =O, —F, —OH) were used as carriers for MnO_x particles. Due to the electronegativity of the terminations, Mn²⁺ was intercalated into the layers and adsorbed on the surface of Ti₃C₂T_x MXene, making the generated Mn₃O₄ particles can firmly anchored, forming the Ti₃C₂@Mn₃O₄ composites. As for the cathode of zinc-ion batteries, Ti₃C₂@Mn₃O₄ was fully converted to Ti₃C₂@ε-MnO₂ during the 1st charge process. Thanks to the excellent conductivity and layered structure of Ti₃C₂T_x MXene, Ti₃C₂@ε-MnO₂ cathode presents excellent kinetic properties and electrochemical performance with a high specific capacity of 440 mA·h·g⁻¹ and high energy density (607 W·h·kg⁻¹) at 0.2 C (1 C=308 mA·h·g⁻¹), and the capacities increase from 270 mA·h·g⁻¹ to 480 mA·h·g⁻¹ after 150 cycles at 1 C. Excellent electrochemical performance, simple material preparation methods, combined with the low cost, high safety and easy assembly characteristics, enable the possible application of rechargeable aqueous Zn-MnO_x batteries in large-scale energy storage.
- rechargeable aqueous zinc-ion battery /
- Mn₃O₄ /
- Ti₃C₂T_x MXene /
- Ti₃C₂@ε-MnO₂ cathode /
- rechargeable battery

HTML全文

图 1 Ti₃AlC₂、Ti₃C₂T_x 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, Ti₃C₂T_x 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

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图 2 Ti₃AlC₂ MAX (a)、Ti₃C₂T_x 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), Ti₃C₂T_x MXene (b); TEM images ((c)-(e)) and HRTEM image (f) of Ti₃C₂@Mn₃O₄; Corresponding elemental mappings of Mn, O, Ti and C (g)

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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

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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

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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

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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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