Cu2+掺杂MnO2作为水系锌离子电池正极材料的合成与电化学性能

doi:10.11949/0438-1157.20210376

摘要/Abstract

摘要：

采用简单的一步电沉积方法制备了Cu²⁺掺杂的MnO₂材料。通过XRD、SEM、TEM等方法对材料进行了表征，结果表明其具有蓬松多孔的纳米结构，作为电池正极材料时有利于Zn²⁺的存储，具有较高的电池容量。与未掺杂样品相比Cu²⁺掺杂的MnO₂材料有更好的电化学性能，在电流密度为200 mA/g时，比容量达到235 mAh/g，增加了47.8%，阻抗也由997.3 Ω降到了564.3 Ω。

关键词: 铜掺杂, 锌离子电池, 正极材料, 纳米结构

Abstract:

In this paper, a simple one-step electrodeposition method was used to prepare Cu²⁺-doped MnO₂ materials. A series of examinations such as XRD, SEM and TEM are employed to describe the characteristic of Cu²⁺ doped MnO₂ samples. As a result, the Cu²⁺ doped MnO₂ materials possess a fluffy porous nanostructure and exhibit enhanced electrochemical performance when as a cathode of aqueous zinc ion batteries. In detail, the specific capacity of Cu²⁺ doped MnO₂ samples exhibit 235 mAh/g in 200 mA/g, which is about 47.8% higher than that of pure MnO₂ sample. Furthermore, the impedance of Cu²⁺ doped MnO₂ is also reduced from 997.3 Ω to 564.3 Ω.

Key words: copper doping, zinc ion battery, cathode material, nanostructure

中图分类号:

TQ 152

张璐璐,谭伯川,李文坡. Cu²⁺掺杂MnO₂作为水系锌离子电池正极材料的合成与电化学性能[J]. 化工学报, 2021, 72(10): 5402-5411.

Lulu ZHANG,Bochuan TAN,Wenpo LI. Synthesis and electrochemical properties of Cu²⁺-doped MnO₂ as cathode materials for aqueous zinc ion batteries[J]. CIESC Journal, 2021, 72(10): 5402-5411.

图/表 10

图1 二氧化锰制备过程示意图

Fig.1 Schematic diagram of the preparation process of manganese dioxide

图2 掺杂前后物相XRD谱图

Fig.2 XRD patterns of MnO2 and Cu0.12MnO2

图3 MnO2和Cu0.12MnO2的形貌和元素分布

Fig.3 Morphology and element distribution of MnO2 and Cu0.12MnO2

图4 Cu0.12MnO2样品N2物理吸附等温线和等效孔径分布(插图)

Fig.4 N2 physisorption isotherms and equivalent pore size distribution (inset) of the Cu0.12MnO2

图5 Cu0.12MnO2样品中Mn (a)和Cu (b)的ICP图；Cu0.12MnO2的EDS图(c)

Fig.5 ICP maps of Mn (a) and Cu (b) of Cu0.12MnO2 samples; EDS diagram of Cu0.12MnO2 (c)

图6 MnO2和Cu0.12MnO2 材料的 CV曲线(a)；200 mA/g下GCD曲线(b)；不同电流密度下GCD曲线(c)；EIS曲线对比(d)

Fig.6 CV curves (a),GCD curves at 200 mA/g (b), GCD curves at different current densities (c) and EIS curves (d) of MnO2 and Cu0.12MnO2

图7 Cu0.12MnO2不同扫速下的CV图 (a)，电化学动力学分析图(b)，GITT(c)及扩散系数分析图(d)；MnO2的GITT(e)及扩散系数分析图(f)

Fig.7 CV diagram at different sweep speeds (a) , electrochemical kinetic analysis diagram (b) and GITT (c) and diffusion coefficient analysis (d) of Cu0.12MnO2； GITT (e) and diffusion coefficient analysis (f) of MnO2

图8 Cu0.12MnO2中Cu的XPS谱图 (a)；掺杂前后Mn的XPS谱图(b)；充电和放电状态下Mn(c)和 Zn(d)的XPS谱图

Fig.8 XPS of Cu in Cu0.12MnO2 (a); XPS of Mn before and after doping (b); XPS of Mn (c) and Zn (d) under charging and discharging conditions respectively

图9 MnO2和Cu0.12MnO2的循环对比图(a)；Ragone图(b)；MnO2 (c)和Cu0.12MnO2 (d)点灯应用图

Fig.9 Cyclic comparison of MnO2 and Cu0.12MnO2 (a) ; Ragone plot of the Zn//Cu2+ doped MnO2 aqueous battery(b); MnO2 (c)and Cu0.12MnO2 (d) lighting application diagram

图10 循环100圈后的Cu0.12MnO2的SEM图(a)和EDS图(b)

Fig.10 SEM image (a) and EDS spera (b) of Cu0.12MnO2 sample after 100 cycles

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Cu²⁺掺杂MnO₂作为水系锌离子电池正极材料的合成与电化学性能

Synthesis and electrochemical properties of Cu²⁺-doped MnO₂ as cathode materials for aqueous zinc ion batteries

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