自支撐二維Ti3C2Tx(MXene)薄膜電化學性能

武偉; 王恩會; 楊濤; 侯新梅

doi:10.13374/j.issn2095-9389.2020.12.05.001

自支撐二維Ti₃C₂T_x(MXene)薄膜電化學性能

doi: 10.13374/j.issn2095-9389.2020.12.05.001

北京科技大學鋼鐵共性技術協同創新中心，北京 100083

基金項目: 國家杰出青年基金資助項目（52025041）；國家自然科學基金資助項目（51904021，51902020）；中央高校基本科研業務費資助項目（FRF-TP-19-004B2Z，FRF-TP-18-045A1）

詳細信息

通訊作者:
E-mail：yangtaoustb@ustb.edu.cn

中圖分類號: TQ134.1+1
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出版歷程
- 收稿日期: 2020-12-05
- 刊出日期: 2021-06-25

Electrochemical performance of self-assembled two-dimensional Ti₃C₂T_x(MXene) thin films

Collaborative Innovation Center of Steel Technology, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: yangtaoustb@ustb.edu.cn

摘要

摘要: 采用LiF?HCl混合溶液刻蝕法刻蝕Ti₃AlC₂得到Ti₃C₂T_x(MXene)膠體溶液，通過真空抽濾法抽濾MXene膠體溶液得到柔性MXene薄膜。使用X射線衍射(XRD)、掃描電子顯微鏡(SEM)、能量色散譜(EDS)和X射線光電子能譜(XPS)等方法表征MXene的物相、形貌及化學元素，并采用循環伏安、恒電流充放電、交流阻抗法等電化學測試手段研究MXene薄膜電極的電化學性能。研究顯示：當電解液為H₂SO₄，MXene薄膜的厚度為6.6 μm時，在5 mV·s^?1掃速下質量比電容達到228 F·g^?1；同時隨著掃速從5 mV·s^?1提升至100 mV·s^?1時，電容保持率為51%，是40.2 μm厚度MXene薄膜電極的3倍。該研究展示酸性電解液和較薄的薄膜厚度有利于提高MXene材料基超級電容器的性能。
- MXene /
- 二維材料 /
- 薄膜 /
- 電化學性能 /
- 電解液 /
- 厚度
Abstract: With the rapid growth in the demand for portable/wearable electronic products, the demand for high-performance, flexible, and lightweight power is becoming stronger. Given the excellent cyclic stability, high rate of charge/discharge, and high power density of supercapacitors, they have become ideal devices to meet the power requirements of portable/wearable electronic products. The most effective method to enhance supercapacitor performance is to improve the electrode materials. Lately, researchers have concentrated on exploring and developing excellent-performance electrode materials. Two-dimensional (2D) materials are the most prospective supercapacitor materials owing to their outstanding properties. Transition-metal carbides and nitrides (MXene), a novel family of 2D materials, have been found to exhibit relatively better chemical stability, higher surface area and active surface sites, excellent hydrophilicity, and higher electrical conductivity. The earliest explored and the most widely applied MXene is Ti₃C₂T_x. In several types of energy-storage systems, such as electrochemical hydrogen storage, supercapacitors, and lithium-ion batteries, Ti₃C₂T_x has shown exceptional performance as potential electrode material. In this work, Ti₃C₂T_x colloidal solution was prepared by etching Ti₃AlC₂ with a LiF–HCl mixed solution and a flexible MXene film was obtained via vacuum filtration. The physical structures and morphologies of graphene and chemical elements were characterized via X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The capacitance properties of the MXene film electrode were studied via cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The research shows that in H₂SO₄ electrolyte, the MXene film thickness is 6.6 μm, and the mass-specific capacitance can reach 228 F·g^?1 at 5 mV·s^?1. When the scanning speed increases to 100 mV·s^?1, the capacitance retention rate can reach 51%, which is three times that of the 40.2 μm MXene film electrode. The research shows that acidic electrolyte and thin film are beneficial to improve the performance of MXene supercapacitors.
- MXene /
- 2D materials /
- film /
- electrochemical properties /
- electrolyte /
- thickness

HTML全文

圖 1 （a）Ti₃AlC₂、MXene沉淀和MXene薄膜的X射線衍射圖；（b）MXene薄膜的XPS全譜圖

Figure 1. (a) XRD patterns of Ti₃AlC₂, MXene sediment, and MXene films; (b) XPS profiles of MXene film

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圖 2 MXene薄膜的實物照片和掃描電鏡圖。（a）展開；（b）卷在玻璃棒上；（c）Ti₃AlC₂；（d）MXene沉淀；（e）MXene薄膜頂視圖；（f）MXene薄膜截面圖；（g）MXene-1薄膜；（h）MXene-2薄膜；（i）MXene-3薄膜

Figure 2. Photoes and SEM image of MXene film: (a) unfolding; (b) rolled on a glass rod; (c) Ti₃AlC₂; (d) MXene sediment; (e) MXene film; (f) cross-sectional image of MXene film; (g) MXene-1 film; (h) MXene-2 film; (i) MXene-3 film

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圖 3 MXene薄膜的表面元素分布。（a）MXene薄膜；（b）Ti；（c）C；（d）O；（e）F；（e）Cl

Figure 3. Distribution of elements of MXene film: (a) MXene film; (b) Ti; (c) C; (d) O; (e) F; (e) Cl

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圖 4 （a）MXene-1在H₂SO₄、KOH、Na₂SO₄電解液中在5 mV· s^?1時的循環伏安曲線；（b）在H₂SO₄、KOH、Na₂SO₄電解液中MXene薄膜的交流阻抗譜圖

Figure 4. (a) CV curves of MXene-1 in H₂SO₄, KOH, and Na₂SO₄ at 5 mV·s^?1; (b) EIS spectra of MXene film electrodes in H₂SO₄, KOH, and Na₂SO₄

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圖 5 MXene-1在H₂SO₄（a）、KOH（b）、Na₂SO₄（c）電解液中在不同掃描速度下的循環伏安曲線；（d）在不同電解液中比電容隨掃速的變化

Figure 5. CV curves of MXene-1 electrode with different scan rates in H₂SO₄ (a), KOH (b), and Na₂SO₄ (c); (d) specific capacitance of MXene-1 electrode vs scan rate

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圖 6 MXene-1在H₂SO₄（a）、KOH（b）和Na₂SO₄（c）電解液中，在不同充放電電流密度下的充放電曲線

Figure 6. GCDs of MXene-1 electrode with different current densities in H₂SO₄ (a), KOH (b), and Na₂SO₄ (c)

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圖 7 （a）不同厚度的MXene薄膜在掃描速度5 mV·s^?1時循環伏安曲線；（b）不同厚度的MXene薄膜的交流阻抗譜圖

Figure 7. (a) CV curves of MXene film with different thicknesses at 5 mV·s^?1; (b) EIS spectra of MXene film electrodes

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圖 8 不同厚度的MXene薄膜比電容隨掃描速率變化圖（a）和在電流密度為1 A·g^?1的充放電曲線（b）

Figure 8. Specific capacitance vs scan rate (a) and GCDs at 1 A·g^?1 (b) of MXene electrode with different thicknesses

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參考文獻(29)

[1]	Kim B C, Hong J Y, Wallace G G, et al. Recent progress in flexible electrochemical capacitors: electrode materials, device configuration, and functions. Adv Energy Mater, 2015, 5(22): 1500959 doi: 10.1002/aenm.201500959
[2]	Yan P T, Zhang R J, Jia J, et al. Enhanced supercapacitive performance of delaminated two-dimensional titanium carbide/carbon nanotube composites in alkaline electrolyte. J Power Sources, 2015, 284: 38 doi: 10.1016/j.jpowsour.2015.03.017
[3]	Lin T Q, Chen I W, Liu F X, et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science, 2015, 350(6267): 1508 doi: 10.1126/science.aab3798
[4]	Zhang Y, Chang C R, Wang S W, et al. Preparation and supercapacitive performance of pinecone-like NiMoO₄/MnO₂ composite material. Chin J Eng, 2019, 41(5): 646 張勇, 常翠榮, 王詩文, 等. 類松果狀NiMoO₄/MnO₂復合材料的合成及超級電容性能. 工程科學學報, 2019, 41(5):646
[5]	Yang T, Liu H J, Bai F, et al. Supercapacitor electrode based on few-layer h-BNNSs/rGO composite for wide-temperature-range operation with robust stable cycling performance. Int J Miner Metall Mater, 2020, 27(2): 220 doi: 10.1007/s12613-019-1910-x
[6]	Tan C L, Cao X H, Wu X J, et al. Recent advances in ultrathin two-dimensional nanomaterials. Chem Rev, 2017, 117(9): 6225 doi: 10.1021/acs.chemrev.6b00558
[7]	Naguib M, Kurtoglu M, Presser V, et al. Two-dimensional nanocrystals produced by exfoliation of Ti₃AlC₂. Adv Mater, 2011, 23(37): 4248 doi: 10.1002/adma.201102306
[8]	Xia Q X, Fu J J, Yun J M, et al. High volumetric energy density annealed-MXene-nickel oxide/MXene asymmetric supercapacitor. RSC Adv, 2017, 7(18): 11000 doi: 10.1039/C6RA27880A
[9]	Couly C, Alhabeb M, Van Aken K L, et al. Asymmetric flexible mxene-reduced graphene oxide micro-supercapacitor. Adv Electron Mater, 2018, 4(1): 1700339 doi: 10.1002/aelm.201700339
[10]	Hu Q K, Sun D D, Wu Q H, et al. MXene: a new family of promising hydrogen storage medium. J Phys Chem A, 2013, 117(51): 14253 doi: 10.1021/jp409585v
[11]	Boota M, Anasori B, Voigt C A, et al. Pseudocapacitive electrodes produced by oxidant-free polymerization of pyrrole between the layers of 2D titanium carbide (MXene). Adv Mater, 2016, 28(7): 1517 doi: 10.1002/adma.201504705
[12]	Ghidiu M, Kota S, Halim J, et al. Alkylammonium cation intercalation into Ti₃C₂ (MXene): effects on properties and ion-exchange capacity estimation. Chem Mater, 2017, 29(3): 1099 doi: 10.1021/acs.chemmater.6b04234
[13]	Ghidiu M, Lukatskaya M R, Zhao M Q, et al. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature, 2014, 516(7529): 78 doi: 10.1038/nature13970
[14]	Mashtalir O, Lukatskaya M R, Kolesnikov A I, et al. The effect of hydrazine intercalation on the structure and capacitance of 2D titanium carbide (MXene). Nanoscale, 2016, 8(17): 9128 doi: 10.1039/C6NR01462C
[15]	Wen Y Y, Rufford T E, Chen X Z, et al. Nitrogen-doped Ti₃C₂T_x MXene electrodes for high-performance supercapacitors. Nano Energy, 2017, 38: 368 doi: 10.1016/j.nanoen.2017.06.009
[16]	Zhao M Q, Ren C E, Ling Z, et al. Flexible MXene/carbon nanotube composite paper with high volumetric capacitance. Adv Mater, 2015, 27(2): 339 doi: 10.1002/adma.201404140
[17]	Ren Y Y, Zhu J F, Wang L, et al. Synthesis of polyaniline nanoparticles deposited on two-dimensional titanium carbide for high-performance supercapacitors. Mater Lett, 2018, 214: 84 doi: 10.1016/j.matlet.2017.11.060
[18]	Xu S K, Wei G D, Li J Z, et al. Binder-free Ti₃C₂T_x MXene electrode film for supercapacitor produced by electrophoretic deposition method. Chem Eng J, 2017, 317: 1026 doi: 10.1016/j.cej.2017.02.144
[19]	Tang Y, Zhu J F, Wu W L, et al. Synthesis of nitrogen-doped two-dimensional Ti₃C₂ with enhanced electrochemical performance. J Electrochem Soc, 2017, 164(4): A923 doi: 10.1149/2.0041706jes
[20]	Yang C H, Que W X, Yin X T, et al. Improved capacitance of nitrogen-doped delaminated two-dimensional titanium carbide by urea-assisted synthesis. Electrochim Acta, 2017, 225: 416 doi: 10.1016/j.electacta.2016.12.173
[21]	Huang Y Y, Li G H, Zhao B, et al. Preparation and energy storage properties of V₂O₅/MXene nanocomposites. Chin J Eng, 2020, 42(8): 1018 黃瑩瑩, 李庚輝, 趙博, 等. V₂O₅/MXene納米復合材料制備及儲能性能. 工程科學學報, 2020, 42(8):1018
[22]	Naguib M, Halim J, Lu J, et al. New two-dimensional niobium and vanadium carbides as promising materials for Li-ion batteries. J Am Chem Soc, 2013, 135(43): 15966 doi: 10.1021/ja405735d
[23]	Ahmed B, Anjum D H, Gogotsi Y, et al. Atomic layer deposition of SnO₂ on MXene for Li-ion battery anodes. Nano Energy, 2017, 34: 249 doi: 10.1016/j.nanoen.2017.02.043
[24]	Zhao M Q, Torelli M, Ren C E, et al. 2D titanium carbide and transition metal oxides hybrid electrodes for Li-ion storage. Nano Energy, 2016, 30: 603 doi: 10.1016/j.nanoen.2016.10.062
[25]	Naguib M, Kurtoglu M, Presser V, et al. Two-dimensional nanocrystals: two-dimensional nanocrystals produced by exfoliation of Ti₃AlC₂. Adv Mater, 2011, 23(37): 4207 doi: 10.1002/adma.201190147
[26]	Lukatskaya M R, Bak S M, Yu X Q, et al. Probing the mechanism of high capacitance in 2D titanium carbide using in situ X-ray absorption spectroscopy. Adv Energy Mater, 2015, 5(15): 1500589 doi: 10.1002/aenm.201500589
[27]	Li H Y, Hou Y, Wang F X, et al. Flexible all-solid-state supercapacitors with high volumetric capacitances boosted by solution processable MXene and electrochemically exfoliated graphene. Adv Energy Mater, 2017, 7(4): 1601847 doi: 10.1002/aenm.201601847
[28]	Singh S K, Dhavale V M, Boukherroub R, et al. N-doped porous reduced graphene oxide as an efficient electrode material for high performance flexible solid-state supercapacitor. Appl Mater Today, 2017, 8: 141 doi: 10.1016/j.apmt.2016.10.002
[29]	Mashtalir O, Lukatskaya M R, Zhao M Q, et al. Amine-assisted delamination of Nb₂C MXene for Li-ion energy storage devices. Adv Mater, 2015, 27(23): 3501 doi: 10.1002/adma.201500604