一步法合成二维Ti3C2及其电化学性能研究

doi:10.11949/0438-1157.20210549

摘要/Abstract

摘要：

二维过渡金属碳/氮化物（MXene）是一种新型二维材料，可通过从MAX相前体中选择性刻蚀 A 原子层获得。在传统制备MXene的方法中，常用的刻蚀剂是氢氟酸。然而高浓度氢氟酸的使用，不可避免会带来安全问题，甚至破坏MXene的晶体结构，从而限制本征物理化学性能。从典型的碳化物前体Ti₃AlC₂出发，使用 NH₄BF₄作为刻蚀剂，有效降低体系中酸的使用量；在反应过程中，刻蚀 A 层的同时， $N H 4 +$ 进入堆垛层间，扩大层间距，弱化层间作用力。因此，仅通过简单手摇就可以实现高效剥离，得到具有完整晶体结构的二维Ti₃C₂。进一步测试了Ti₃C₂的电化学性能，结果显示，所得的Ti₃C₂具有优异的性能（扫描速率为5 mV?s^-1时为503 F?g^-1）和循环稳定性（在5 A?g^-1下循环10⁴次后电容保持率为95.8%）。本文为Ti₃C₂纳米片的合成及应用提供了新的思路。

关键词: 水热, 纳米材料, 合成, Ti₃C₂纳米片, 电化学, MXene

Abstract:

Two-dimensional transition metal carbides and carbonitrides (MXenes) are the latest additions of the 2D world, which can be obtained by selective etching the a atomic layers from layered MAX precursors. In the traditional method of preparing MXene, the commonly used etchant is hydrofluoric acid. However, the use of concentrated hydrofluoric acid may inevitably bring about safety problems and even the destruction of crystal structure, resulting in the deterioration of intrinsic physical and chemical properties. This article starts from the typical carbide precursor Ti₃AlC₂and uses NH₄BF₄ as an etchant to effectively reduce the amount of acid used in the system. More importantly, during the reaction process, the A layers were etched accompanied by intercalation of $N H 4 +$ , by which the interlayer spacing was expanded and interlayer interaction was greatly weakened. High exfoliation efficiency of 2D Ti₃C₂ with intact crystallinities exfoliation was realized by a sequent hand shaking process. The electrochemical performance of as-obtained Ti₃C₂ was further characterized, showing an excellent capacitive electrochemical performance (503 F?g^-1 at a scan rate of 5 mV?s^-1) and cycling stability (the capacitance retention rate is 95.8% at 5 A·g^-1 after 10⁴ cycles). This provides new ideas for the synthesis and application of Ti₃C₂ nanosheets.

Key words: hydrothermal, nanomaterials, synthesis, Ti₃C₂nanosheets, electrochemistry, MXene

中图分类号:

TQ 174

居涛, 李国辉, 耿凤霞. 一步法合成二维Ti₃C₂及其电化学性能研究[J]. 化工学报, 2022, 73(2): 951-959.

Tao JU, Guohui LI, Fengxia GENG. One-step synthesis of two-dimensional Ti₃C₂ and its electrochemical performance[J]. CIESC Journal, 2022, 73(2): 951-959.

图/表 9

图1 Ti3C2纳米片的制备示意图

Fig.1 Schematic diagram of the preparation of Ti3C2 nanosheets

图2 反应前、后样品的结构分析

Fig.2 Sample structure analysis before and after the reaction

图3 反应过程分析表征

Fig.3 Analysis and characterization of the reaction process

图4 手摇剥离之后样品的表征结果

Fig.4 Sample characterization after manual exfoliating

表1 通过不同方法生产的MXene的工艺条件和结果

Table 1 Process conditions and results for MXene produced by different methods

Method	Time/h	Acid concentration/ (mol·L^-1)	Lateral size/μm
this work	8	6	1.5—2.5
LiF/HCl^[24]	45	6	<1.0
NH₄F/HCl^[25]	24	6	—
NaBF₄/HCl^[29]	24	12	—
FeF₃/HCl^[26]	50	6	—

图5 Ti3C2的XPS分析

Fig.5 XPS analysis of Ti3C2

图6 Ti3C2薄膜的导电性测试

Fig.6 Conductivity of Ti3C2 film

图7 Ti3C2电极在1 mol·L-1 H2SO4下的电化学性能

Fig.7 Electrochemical performance of Ti3C2 electrode at 1 mol·L-1 H2SO4

表2 所制备的Ti3C2电极容量以及循环稳定性能与文献中的数据对比

Table 2 The gravimetric capacitance and cycling stability comparisons between designed Ti3C2 and Ti3C2 MXenes reported in literatures

Material

Test conditions

Specific capacitance/

(F?g^-1)

polyaniline/Ti₃C₂^[35]

Ti₃C₂^[36]

Ti₃C₂^[37]

Ti₃C₂^[38]

Ti₃C₂^[39]

Ti₃C₂^[40]

2 mV?s^-1

1 mV?s^-1

5 mV?s^-1

1 A?g^-1

503

500

266.5

228

333.3

231

98.3% for 10⁴ cycles

>99% for 10⁴ cycles

86.4% for 10⁴ cycles

85% for 10³ cycles

97.5% for 5000 cycles

71% for 3000 cycles

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一步法合成二维Ti₃C₂及其电化学性能研究

One-step synthesis of two-dimensional Ti₃C₂ and its electrochemical performance

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