二氧化锰形貌对Ti3C2Tx@MnO2复合材料电化学性能的影响

doi:10.15541/jim20190309

无机材料学报 ›› 2020, Vol. 35 ›› Issue (1): 119-125.DOI: 10.15541/jim20190309

所属专题： MAX相和MXene材料； 2020年能源材料论文精选(二)：超级电容器；【虚拟专辑】超级电容器(2020~2021)

二氧化锰形貌对Ti₃C₂T_x@MnO₂复合材料电化学性能的影响

李学林,朱建锋(),焦宇鸿,黄家璇,赵倩楠

陕西科技大学材料科学与工程学院, 陕西省无机材料绿色制备与功能化重点实验室, 西安 710021

收稿日期:2019-06-26 修回日期:2019-07-31 出版日期:2020-01-20 网络出版日期:2019-10-25
作者简介:李学林(1994-), 女, 博士研究生. E-mail:lxlsust@outlook.com
基金资助:
国家自然科学基金(51572158);陕西科技大学研究生创新基金

Manganese Dioxide Morphology on Electrochemical Performance of Ti₃C₂T_x@MnO₂ Composites

LI Xue-Lin,ZHU Jian-Feng(),JIAO Yu-Hong,HUANG Jia-Xuan,ZHAO Qian-Nan

Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, School of Material Science and Engineering, Shaanxi University of Science and Technology, Xi’an 710021, China

Received:2019-06-26 Revised:2019-07-31 Published:2020-01-20 Online:2019-10-25
About author:LI Xue-Lin(1994-), female, PhD candidate. E-mail:lxlsust@outlook.com
Supported by:
National Natural Science Foundation of China(51572158);Graduate Innovation Fund of Shaanxi University of Science and Technology

摘要/Abstract

摘要：

以聚多巴胺(PDA)修饰的Ti₃C₂T_x为基体, 高锰酸钾(KMnO₄)为锰源, 十六烷基三甲基溴化铵(CTAB)和聚乙二醇(PEG)为表面活性剂, 采用液相共沉淀法及水热法, 制备出四种不同形貌的Ti₃C₂T_x@MnO₂复合材料。通过FE-SEM、XRD、Raman、FT-IR、BET及电化学测试, 系统研究了纳米碎片状(δ-MnO₂)、米粒状(α-MnO₂)、纳米花球状(α-MnO₂)以及纳米线状二氧化锰(α-MnO₂)对Ti₃C₂T_x物相结构、电化学活性和电荷存储机理的影响。结果表明: 纳米线状MnO₂复合改性的Ti₃C₂T_x比表面积最大、电荷转移阻抗最小且循环稳定性最优, 在扫描速率为2 mV?s ^-1时的比容量达340.9 F?g ^-1, 比使用CTAB时高出近2.5倍。

关键词: MXene, 聚多巴胺, 表面活性剂, 二氧化锰, 电化学性能

Abstract:

Ti₃C₂T_x@MnO₂ composites with different morphologies were prepared by liquid-phase coprecipitation and hydrothermal method using Ti₃C₂T_x@PDA as matrix, KMnO₄ as manganese source, CTAB or PEG as surfactant. Effect of MnO₂ morphology (δ-MnO₂ nanofragments, α-MnO₂ nanorods, α-MnO₂ nanoflowers and α-MnO₂ nanowires) on phase structure and electrochemical performance of Ti₃C₂T_x was analyzed by FE-SEM, XRD, Raman, FT-IR, BET, and electrochemical measurements. The results show that Ti₃C₂T_x@α-MnO₂ nanowires possesses better comprehensive electrochemical properties (340.9 F?g ^-1 at 2 mV?s ^-1), nearly 2.5 times higher than using CTAB, and smaller charge transfer resistance, as well as excellent cycle stability.

Key words: MXene, polydopamine, surfactant, manganese dioxide, electrochemical performance

中图分类号:

TB333

李学林, 朱建锋, 焦宇鸿, 黄家璇, 赵倩楠. 二氧化锰形貌对Ti₃C₂T_x@MnO₂复合材料电化学性能的影响[J]. 无机材料学报, 2020, 35(1): 119-125.

LI Xue-Lin, ZHU Jian-Feng, JIAO Yu-Hong, HUANG Jia-Xuan, ZHAO Qian-Nan. Manganese Dioxide Morphology on Electrochemical Performance of Ti₃C₂T_x@MnO₂ Composites[J]. Journal of Inorganic Materials, 2020, 35(1): 119-125.

图/表 7

图1 样品的FE-SEM照片 (a) Pure Ti3C2Tx; (b) Ti3C2Tx@PDA; (c) Ti3C2Tx@δ-MnO2 nanofragments; (d) Ti3C2Tx@α-MnO2 nanorods; (e) Ti3C2Tx@α-MnO2 nanoflowers; (f) Ti3C2Tx@α-MnO2 nanowires

Fig. 1 FE-SEM mages of the samples

图2 Ti3C2Tx@PDA的FE-SEM照片(a)、TEM照片(b)及EDS图谱(c-f)

Fig. 2 FE-SEM images (a), TEM images (b) and EDS mappings (c-f) of Ti3C2Tx@PDA

图3 样品的XRD图谱(a)和相应的局部放大图(b) (1) Pure Ti3C2Tx; (2) Ti3C2Tx@PDA; (3) Ti3C2Tx@δ-MnO2 nanofragments; (4) Ti3C2Tx@α-MnO2 nanorods; (5) Ti3C2Tx@α-MnO2 nanoflowers; (6) Ti3C2Tx@α-MnO2 nanowires

Fig. 3 XRD patterns of samples (a) and corresponding drawing of partial enlargement (b)

图4 样品的Raman图谱(a)、FT-IR图谱(b)、N2吸附/脱附曲线(c)和孔径分布图(d) (1-black): Pure Ti3C2Tx; (2-red) Ti3C2Tx@PDA; (3-navy) Ti3C2Tx@δ-MnO2 nanofragments; (4-purple) Ti3C2Tx@α-MnO2 nanorods; (5-green) Ti3C2Tx@α-MnO2 nanoflowers; (6-blue) Ti3C2Tx@α-MnO2 nanowires

Fig. 4 Raman spectra (a), FT-IR spectra (b), Nitrogen sorption isotherms (c) and pore size distributions (d) of samples

图5 纳米线状Ti3C2Tx@α-MnO2在不同扫描速率下的CV曲线(a)和不同电流密度下的GCD曲线(b)

Fig. 5 CV curves at different scan rate (a) and GCD curves at different current densities (b) of Ti3C2Tx@α-MnO2 nanowires

图6 样品的电化学性能 (a) CV curves at 50 mV?s-1; (b) GCD curves at 1 A?g-1; (c) Specific capacitances at various scan rates; (d) Nyquist plots; (e) Equivalent circuit adopted in the simulation of EIS spectra; (f) Cycling stability measured at 3 A?g-1 Pure Ti3C2Tx (black); Ti3C2Tx@PDA (red); Ti3C2Tx@δ-MnO2 nanofragments (navy); Ti3C2Tx@α-MnO2 nanorods (purple); Ti3C2Tx@α-MnO2 nanoflowers (green); Ti3C2Tx@α-MnO2 nanowires (blue)

Fig. 6 Electrochemical performance of samples

表1 各样品的电化学阻抗谱EIS数据拟合值

Table 1 Details of various parameters based Spectroscopy Impedance on the equivalent circuit derived by fitting Electrochemical (EIS) data of prepared samples

Sample	R_e/Ω	C_dl/μF	R_ct/Ω	Z_w/(Ω^-1?s^1/2)	C_L/mF
Ti₃C₂T_x	2.043	12.04	0.4575	0.04459	39.82
Ti₃C₂T_x@PDA	2.397	43.26	0.4671	0.09429	65.16
Ti₃C₂T_x@δ-MnO₂ nanofragments	2.678	187.1	1.333	0.0999	343.5
Ti₃C₂T_x@α-MnO₂ nanorods	2.989	31.7	1.358	0.04104	263.1
Ti₃C₂T_x@α-MnO₂ nanoflowers	2.304	20.89	1.925	0.001071	65.97
Ti₃C₂T_x@α-MnO₂ nanowires	2.592	135.3	1.268	0.1547	373.5

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二氧化锰形貌对Ti₃C₂T_x@MnO₂复合材料电化学性能的影响

Manganese Dioxide Morphology on Electrochemical Performance of Ti₃C₂T_x@MnO₂ Composites

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