纺织学报 ›› 2022, Vol. 43 ›› Issue (05): 77-85.doi: 10.13475/j.fzxb.20210504109

• 纤维材料 • 上一篇    下一篇

电化学沉积锌电池MnOx/碳纳米纤维膜自支撑正极的制备及其电化学特性

杨科1, 闫俊1, 肖勇2, 徐晶3, 陈磊1(), 刘雍1   

  1. 1.天津工业大学 纺织科学与工程学院, 天津 300387
    2.山东非金属材料研究所, 山东 济南 250031
    3.泉州海关综合技术服务中心, 福建 泉州 362000
  • 收稿日期:2021-05-17 修回日期:2022-01-05 出版日期:2022-05-15 发布日期:2022-05-30
  • 通讯作者: 陈磊
  • 作者简介:杨科(1995—),男,硕士。主要研究方向为锌离子电池正极材料。
  • 基金资助:
    中国博士后科学基金特别资助项目(2019T120189);中国博士后科学基金面上一等资助项目(2018M640240)

Preparation of MnOx/carbon nanofiber membrane free-standing cathodes for zinc ion battery based on electrochemical deposition and their electrochemical characteristics

YANG Ke1, YAN Jun1, XIAO Yong2, XU Jing3, CHEN Lei1(), LIU Yong1   

  1. 1. School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China
    2. Institute of Nonmetallic Materials of Shandong, Ji'nan, Shandong 250031, China
    3. Technical Service Center of Quanzhou Customs, Quanzhou, Fujian 362000, China
  • Received:2021-05-17 Revised:2022-01-05 Published:2022-05-15 Online:2022-05-30
  • Contact: CHEN Lei

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摘要：

为开发性能优越、制备工艺简单的可充电锌离子电池(ZIBs)正极材料,以静电纺纳米纤维膜为前驱体,经预氧化和高温炭化制备了碳纳米纤维膜(CNFs),并以CNFs为基底,结合电化学沉积法制备了具有皮芯结构的MnOx/CNFs复合材料。探讨了不同电化学沉积时间对MnOx/CNFs复合材料表面形貌、结构以及ZIBs循环充放稳定性和倍率性能等电化学性能的影响。结果表明:电化学沉积法使MnOx活性材料与CNFs基底间界良好结合,减少了活性材料脱附,提高了二者的界面离子和电子传输能力;以沉积2 h的MnOx/CNFs作为正极时,ZIBs在0.1 A/g电流密度下的比容量可达647.9 mA·h/g,且在0.5 A/g电流密度下循环充放电500次后仍能保持221.8 mA·h/g的比容量;经2 A/g电流密度循环充放电后在0.1 A/g电流密度下仍能恢复至初始比容量的94%,具有较好倍率性能。

关键词: 碳纳米纤维膜, 电化学沉积, 静电纺丝, 自支撑材料, 锌离子电池

Abstract:

To develop cathode materials for rechargeable zinc ion batteries (ZIBs) with excellent performance and a simple preparation process, electrospun nanofiber membranes were used as precursors to prepare carbon nanofiber films (CNFs) by pre-oxidation and high-temperature carbonization. MnOx/CNFs composites with the skin-core structure were prepared by using electrochemical deposition method with CNFs as substrate. The effects of electrochemical deposition time on the surface morphology, specific surface area, cyclic charge-discharge stability, and rate performance of MnOx/CNFs composites were discussed. The results show that the electrochemical deposition method promotes a good interfacial bonding between the loaded active material and the CNFs substrate and improves the ion and electron transport capacity at the interface. The specific capacity can reach 647.9 mA·h/g after the activation at the current density of 0.1 A/g. In addition, the ZIBs with MnOx/CNFs cathode via depositing MnOx for 2 h show the specific capacity of 221.8 mA·h/g after 500 cycles under the current density of 0.5 A/g. After cycling of charging and discharging at the current density of 2 A/g, 94% of the initial capacity can still be restored at the current density of 0.1 A/g, which represent excellent performance of MnOx/CNFs cathode.

Key words: carbon nanofiber membrane, electrochemical deposition, electrostatic spinning, free-standing material, zinc ion battery

中图分类号: 

  • TS179

图1

MnOx/CNFs复合材料制备流程示意图及各步骤对应样品形貌演变图"

图2

CNFs、MnOx/CNFs-1、MnOx/CNFs-2和MnOx/CNFs-3的表面和截面SEM和TEM照片"

图3

MnOx/CNFs-2表面Mn元素分布图"

图4

MnOx/CNFs-2的XPS全谱图和Mn2p光谱图"

图5

CNFs和MnOx/CNFs-2的XRD谱图及α-MnO2晶体结构示意图"

图6

N2吸附-脱附等温曲线"

图7

MnOx/CNFs-2复合正极材料的循环伏安曲线"

图8

0.1 A/g电流密度下CNFs、MnOx/CNFs-1、MnOx/CNFs-2、MnOx/CNFs-3第2次循环充放电曲线"

图9

CNFs, MnOx/CNFs-1, MnOx/CNFs-2, MnOx/CNFs-3的电化学性能"

表1

MnOx/CNFs复合膜与其他碳基材料的容量比较"

材料 循环次数 电流密度/(A·g-1) 比容量/(mA·h·g-1) 数据来源
MnOx/碳纳米纤维 50 0.1 ~340 本文
500 0.5 ~200
β-MnO2/C 250 0.2 ~150 [11]
石墨烯 50 0.1 ~20 [16]
石墨烯 800 7 ~87.4 [17]
碳纳米角/碳纳米管 500 3 ~159.1 [19]
MnOx/N-C 600 0.5 ~240 [37]
Mn3O4/C 450 0.5 ~215 [27]
MnO2/碳纳米管 1 000 2.77 ~100 [10]
ZnMn2O4NDs/还原氧化石墨烯 100 0.2 ~207.6 [39]
碳布/MnO2 200 1.2 ~250 [32]
δ-MnO2/石墨烯 100 0.4 ~114.2 [18]
MnO2/石墨烯 10 000 2 ~190 [40]
MnO2/碳纳米管 500 5 ~100 [14]
MnO2/C 50 0.066 ~189 [30]

图10

长时间循环使用前后MnOx/CNFs-2的扫描电镜照片"

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