制备条件对MXene形貌、 结构与电化学性能的影响

doi:10.7503/cjcu20180783

摘要/Abstract

摘要：

以Ti₃AlC₂为原料, 采用LiF+HCl一步刻蚀-插层制备Ti₃C₂T_x, 进一步通过超声处理得到单层或少层的MXene. 利用X射线衍射(XRD)、 X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和电化学测试对样品的结构、形貌和电化学性能进行了研究. 通过改变刻蚀剂的比例及超声剥离时间, 研究了不同刻蚀条件和剥离条件对二维晶体Ti₃C₂T_x的形貌、结构和电化学性能的影响. 结果表明, 制备条件对MXene的片层结构和性能具有较大的影响. 当HCl浓度为6 mol/L, LiF与Ti₃AlC₂的摩尔比为7.5, 超声时间为1 h时, 所得MXene具有较小的晶格常数和较大的片层尺寸, 片层尺寸可达1 μm, 具有较多的表面含氧官能团, 电化学性能最佳, 在0.5 A/g的电流密度下, 质量比容量达到342 F/g, 当电流密度提高至20 A/g时, 质量比容量仍可保持244 F/g, 在1 A/g电流密度下循环10000周后, 容量仍能保留87%左右, 表现出较好的倍率性能与循环稳定性.

关键词: MXene, Ti₃C₂T_x, 刻蚀, 剥离, 电化学性能

Abstract:

Using Ti₃AlC₂ as precursor, multilayered Ti₃C₂T_x were prepared and intercalated in one process with LiF+HCl as etchant, and then single or few layers of two-dimensional(2D) MXene flakes were delaminated with following sonication. The studies were focused on the effects of etching and delamination conditions by tuning the ratios of etchant/Ti₃AlC₂(molar ratio) and the sonication time on the morphologies, structures and electrochemical properties of two dimensional crystal flakes of Ti₃C₂T_x. The results showed that selecting appropriate fabrication conditions is crucial to the structures and properties of MXene flakes. It is shown that the MXene obtained with 6 mol/L HCl, the LiF/Ti₃AlC₂ molar ratio of 7.5 and the sonication time of 1 h which named FMX7.5-6' displayed a small lattice constant and a large flake size up to 1 μm. It also had a high content of oxygen-containing functional groups and demonstrated the best electrochemical properties. At the current density of 0.5 A/g, it demonstrated a high specific capacity of 342 F/g and its capacity could reach 244 F/g at the current density of 20 A/g. The specific capacity could remain 87% of the original value after 10000 cycling test at the current density of 1 A/g, showing a good rate and stability performance.

Key words: MXene, Ti₃C₂T_x, Etching, Exfoliation, Electrochemical property

中图分类号:

O646

TrendMD:

陈耀燕, 赵昕, 王哲, 董杰, 张清华. 制备条件对MXene形貌、结构与电化学性能的影响. 高等学校化学学报, 2019, 40(6): 1249.

CHEN Yaoyan,ZHAO Xin,WANG Zhe,DONG Jie,ZHANG Qinghua. Effects of Preparation Conditions on the Morphologies, Structures and Electrochemical Properties of MXene^†. Chem. J. Chinese Universities, 2019, 40(6): 1249.

图/表 12

Scheme 1 Schematic of preparation process of MXene flakes by etching and delamination

Fig.1 SEM images of Ti3AlC2 powder(A), MMX7.5-6(B), MMX7.5-9(C) and MMX12-6(D) The insets in (B—D) show the multilayered powder in water after handshaking and washing to pH≥6(i) and the dried multilayered powder of Ti3C2Tx(ii).

Fig.2 TEM images of FMX7.5-6(A), FMX7.5-9(B), FMX12-6(C), FMX7.5-6'(D), FMX7.5-9'(E) and FMX12-6'(F)

Fig.3 Particle size distribution of Ti3C2Tx with sonication for the first times(A) and the second times(B) and concentration distribution of colloidal aqueous solutions of Ti3C2Tx obtained after sonicating for the first times(left) and the second times(right)(C)

Fig.4 SEM images of fracture surfaces of the dried films (A) FMX7.5-6; (B) FMX7.5-9; (C) FMX12-6; (D) FMX7.5-6'; (E) FMX7.5-9'; (F) FMX12-6'.

Fig.5 XRD patterns of multilayered MXene powder(A) and the dried films(B)

Fig.6 XPS surveys of FMX7.5-6’(a), FMX7.5-9’(b) and FMX12-6’(c)

Fig.7 C1s(A) and O1s(B) XPS spectra of FMX7.5-6’(a), FMX7.5-9’(b), FMX12-6’(c) and Ti2p(C) and F1s(D) XPS spectra of FMX7.5-6’

Fig.8 CV curves of all the MXene films at a scan rate of 10 mV/s(A) and FMX7.5-6’ at different scan rates(B)

Fig.9 Galvanostatic charge-discharge curves of all the films at a current density of 0.5 A/g(A) and FMX7.5-6' at different current densities(B)

Fig.10 Gravimetric rate performances(A) and Nyquist plots(B) of all the MXene films

Fig.11 Capacitance retention rate of FMX7.5-6' at a current density of 1 A/g

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