同步氨化/碳化法制备MXene/C平面多孔复合电极

doi:10.15541/jim20190298

摘要/Abstract

摘要：

MXene是一种新型二维过渡金属碳/氮化物, 具有优异电化学性能的赝电容型超级电容器电极材料。本研究尝试用同步氨化/碳化制备MXene平面多孔电极。以滤纸为多孔平面模板, 通过浸渍-烘干的手段把MXene固定在滤纸的纤维上, 然后在氨气的气氛中热处理, 得到了MXene/C平面多孔复合电极。分析结果表明: MXene纳米片均匀包覆在由滤纸碳化形成的碳纤维上。当浸渍5次时, 在2 mV/s的扫速下测试, 制备出的复合电极的面积比电容达到403 mF/cm ²。在电流密度为10 mA/cm ²下进行恒流充放电循环测试2500次后, 比电容仍然与初始电容几乎相同, 表现出良好的倍率性能和循环稳定性。在不使用高分子粘合剂和金属集流体的情况下, 同步氨化/碳化法制备出的MXene/C平面多孔复合电极表现出优良的电化学性能。

关键词: MXene, 超级电容器, 制备

Abstract:

As a new class of two-dimensional transition metal carbon/nitride, MXenes have been proven to be a kind of pseudocapacitive supercapacitor electrode materials with excellent electrochemical property, and hold promise in practical use in the near future. In practical applications, it is required to make the electrode materials into planar porous electrodes for capacitor assembly. Herein, a simultaneous ammonization/carbonization method is proposed for the preparation of MXene planar porous electrode. Filter paper was used as a planar porous template, and MXene was coated on the fibers of the filter paper by means of dipping-drying, and then heat-treated in an ammonia atmosphere to obtain MXene/carbon planar porous composite electrodes. Analysis results show that the MXene nanosheets are uniformly coated on the carbonization-derived carbon fibers of the filter paper. When immersed 5 times, the areal capacitance reaches 403 mF/cm ² at a scan rate of 2 mV/s. After the composite electrode was tested for 2500 times in a galvanostatic charge-discharge cycle at a current density of 10 mA/cm ², the capacitance was almost the same as the initial capacitance, showing good rate performance and cycle stability. The MXene/carbon planar porous composite electrodes prepared by simultaneous ammonia/carbonization exhibit excellent electrochemical performance without using either polymer binder or metal current collector.

Key words: MXene, supercapacitor, preparation

中图分类号:

TB321

张天宇, 崔聪, 程仁飞, 胡敏敏, 王晓辉. 同步氨化/碳化法制备MXene/C平面多孔复合电极[J]. 无机材料学报, 2020, 35(1): 112-118.

ZHANG Tian-Yu, CUI Cong, CHENG Ren-Fei, HU Min-Min, WANG Xiao-Hui. Fabrication of Planar Porous MXene/Carbon Composite Electrodes by Simultaneous Ammonization/Carbonization[J]. Journal of Inorganic Materials, 2020, 35(1): 112-118.

图/表 6

图1 (a)Ti3AlC2多孔体、Ti3C2Tx悬浮液的光学照片和TEM照片(插图为MXene悬浮液的丁达尔效应); (b)同步氨化/碳化法制备MXene/C平面多孔电极的过程

Fig. 1 (a) Optical photographs of porous Ti3AlC2 monolith, aqueous suspension and TEM image of Ti3C2Tx MXene with inset showing the Tyndall effect of MXene; and (b) fabrication process of MXene/carbon planar porous electrode by simultaneous ammonization/carbonization

图2 Ti3C2Tx MXene/C平面多孔电极的组成及结构 (a) XRD patterns; (b) Square resistance of planar porous electrode vs immersion times after simultaneous ammonization/carbonization. Inset shows the dependence of MXene load after simultaneous ammonization/carbonization on immersion times

Fig. 2 Composition and structure of Ti3C2Tx MXene/carbon planar porous electrode

图3 Ti3C2Tx平面多孔电极表面的SEM照片(a)和同步氨化/碳化后Ti3C2Tx的高角环形暗场像HAADF照片(b)

Fig. 3 SEM images of surface morphology of Ti3C2Tx MXene planar electrode (a) and High-Angle Annular Dark Field (HAADF) image of Ti3C2Tx MXene after simultaneous ammonization/carbonization (b)

图4 Ti3C2Tx MXene/C平面多孔电极的电容性能 (a-c) Areal capacitance versus voltage with respect to Ag/AgCl; (d) Areal capacitance as a function of scan rate

Fig. 4 Capacitance of Ti3C2Tx MXene/carbon planar porous electrodes

图5 Ti3C2Tx MXene/C平面多孔电极的面积比电容(a)和质量比电容(b)与文献值的比较

Fig. 5 Comparison of areal capacitance (a) and specific capacitance (b) among the values of Ti3C2Tx MXene/carbon planar porous electrode obtained in this work and those in the literature

图6 同步氨化/碳化法制备的Ti3C2Tx MXene/C平面多孔电极的循环稳定性 (a) Relationship between capacitance retention rate and cycle number; (b-c) GCD curves for (b) the first 10 cycles and (c) the last 11 cycles

Fig. 6 Cyclic stability of Ti3C2Tx MXene/carbon planar porous electrode prepared by means of simultaneous ammonization/carbonization

参考文献 51

[1]	MIRÓ P, AUDIFFRED M, HEINE T . An atlas of two-dimensional materials. Chemical Society Reviews, 2014,43(18):6537-6554. DOI URL
[2]	XU M, LIANG T, SHI M , et al.Graphene-like two-dimensional materials.Chemical Reviews 2013,113(5):3766-3798. DOI URL PMID
[3]	CAHANGIROV S, TOPSAKAL M, AKTURK E , et al.Two- and one-dimensional honeycomb structures of silicon and germanium. Physical Review Letters, 2009,102(23):236804. DOI URL PMID
[4]	LALMI B, OUGHADDOU H, ENRIQUEZ H , et al.Epitaxial growth of a silicene sheet. Applied Physics Letters, 2010,97(22):223109. DOI URL PMID
[5]	LIU H, NEAL A T, ZHU Z , et al.Phosphorene: an unexplored 2D semiconductor with a high hole mobility.ACS Nano, 2014,8(4):4033-4041. DOI URL PMID
[6]	ATACA C, SAHIN H, CIRACI S . Stable, single-layer MX₂ transition- metal oxides and dichalcogenides in a honeycomb-like structure. Journal of Physical Chemistry C, 2012,116(16):8983-8999. DOI URL
[7]	ZHOU Y C, XIANG H M, WANG X H , et al.Electronic structure and mechanical properties of layered compound YB₂C₂: a promising precursor for making two dimensional (2D) B₂C₂ nets.Journal of Materials Science & Technology, 2017,33(9):1044-1054. DOI URL PMID
[8]	NICOLOSI V, CHHOWALLA M, KANATZIDIS M G , et al.Liquid exfoliation of layered materials.Science, 2013,340(6139):1226419. DOI URL PMID
[9]	NAGUIB M, KURTOGLU M, PRESSER V , et al.Two-dimensional nanocrystals produced by exfoliation of Ti₃AlC₂.Advanced Materials, 2011,23(37):4248-4253. DOI URL PMID
[10]	MICHAEL N, OLHA M, JOSHUA C , et al.Two-dimensional transition metal carbides.ACS Nano, 2012,6(2):1322-1331. DOI URL PMID
[11]	ZHANG X, XU J, WANG H , et al.Ultrathin nanosheets of MAX phases with enhanced thermal and mechanical properties in polymeric compositions: Ti₃Si_0.75Al_0.25C₂..Angewandte Chemie-International Edition, 2013,52(16):4361-4365. DOI URL PMID
[12]	MASHTALIR O, NAGUIB M, DYATKIN B , et al.Kinetics of aluminum extraction from Ti₃AlC₂ in hydrofluoric acid..Materials Chemistry and Physics, 2013,139(1):147-152. DOI URL
[13]	GHIDIU M, NAGUIB M, SHI C , et al.Synthesis and characterization of two-dimensional Nb₄C₃(MXene). Chemical Communications, 2014,50(67):9517-9520. DOI URL
[14]	ZHOU J, ZHA X H, CHEN F Y , et al.A two-dimensional zirconium carbide by selective etching of Al₃C₃ from nanolaminated Zr₃Al₃C₅.Angewandte Chemie-International Edition, 2016,55(16):5008-5013. DOI URL PMID
[15]	ANASORI B, LUKATSKAYA MR, GOGOTSI Y . 2D metal carbides and nitrides (MXenes) for energy storage. Nature Reviews Materials, 2017,2(2):16098. DOI URL PMID
[16]	KHAZAEI M, RANJBAR A, ARAI M , et al.Electronic properties and applications of MXenes: a theoretical review..Journal of Materials Chemistry C, 2017,5(10):2488-2503. DOI URL PMID
[17]	ZHU J, HA E, ZHAO G , et al.Recent advance in MXenes: a promising 2D material for catalysis, sensor and chemical adsorption..Coordination Chemistry Reviews, 2017,352:306-327. DOI URL
[18]	HANTANASIRISAKUL K, GOGOTSI Y . Electronic and optical properties of 2D transition metal carbides and nitrides (MXenes). Advanced Materials, 2018,30(52):1804779. DOI URL PMID
[19]	LI X, WANG C, CAO Y , et al.Functional MXenes materials: progress of their applications..Chemistry-An Asian Journal, 2018,13(19):2742-2757. DOI URL PMID
[20]	LIN H, CHEN Y, SHI J . Insights into 2D MXenes for versatile biomedical applications: current advances and challenges ahead. Advanced Science, 2018,5(10):1800518. DOI URL PMID
[21]	WANG H, WU Y, YUAN X , et al.Clay-inspired MXene-based electrochemical devices and photo-electrocatalyst: state-of-the-art progresses and challenges..Advanced Materials, 2018,30(12):1704561. DOI URL PMID
[22]	DIAO J Y, HU M M, LIAN Z , et al.Ti₃C₂T_x MXene catalyzed ethylbenzene dehydrogenation: active sites and mechanism exploration from both experimental and theoretical aspects.ACS Catalysis, 2018,8(11):10051-10057. DOI URL
[23]	YOON Y, LEE K, LEE H . Low-dimensional carbon and MXene- based electrochemical capacitor electrodes. Nanotechnology, 2016,27(17):172001. DOI URL PMID
[24]	ZHANG X, ZHANG Z, ZHOU Z . MXene-based materials for electrochemical energy storage. Journal of Energy Chemistry, 2018,27(1):73-85. DOI URL PMID
[25]	PANG J, MENDES R G, BACHMATIUK A , et al.Applications of 2D MXenes in energy conversion and storage systems..Chemical Society Reviews, 2019,48(1):72-133. DOI URL PMID
[26]	YANG Q, WANG Y, LI X , et al.Recent progress of MXene-based nanomaterials in flexible energy storage and electronic devices..Energy & Environmental Materials, 2018,1(4):183-195. DOI URL PMID
[27]	WANG X H, ZHOU Y C . Solid-liquid reaction synthesis of layered machinable Ti₃AlC₂ ceramic. Journal of Materials Chemistry, 2002,12(3):455-460. DOI URL
[28]	CHENG R F, HU T, ZHANG H , et al.Understanding the lithium storage mechanism of Ti₃C₂T_x MXene.Journal of Physical Chemistry C, 2019,123(2):1099-1109. DOI URL
[29]	HU M M, CUI C, SHI C , et al.High-energy-density hydrogen-ion- rocking-chair hybrid supercapacitors based on Ti₃C₂T_x MXene and carbon nanotubes mediated by redox active molecule.ACS Nano, 2019,13(6):6899-6905. DOI URL PMID
[30]	HU M M, LI Z J, ZHANG H , et al.Self-assembled Ti₃C₂T_x MXene film with high gravimetric capacitance.Chemical Communications, 2015,51(70):13531-13533. DOI URL PMID
[31]	HU M M, LI Z J, LI G X , et al.All-solid-state flexible fiber-based MXene supercapacitors. Advanced Materials Technology, 2017,2(10):1700143.
[32]	HU M M, HU T, CHENG R F , et al.MXene-coated silk-derived carbon cloth toward flexible electrode for supercapacitor application. Journal of Energy Chemistry, 2018,27(1):161-166. DOI URL PMID
[33]	HU M M, LI Z J, HU T , et al.High-capacitance mechanism for Ti₃C₂T_x MXene by in situ electrochemical Raman spectroscopy investigation.ACS Nano, 2016,10(12):11344-11350. DOI URL PMID
[34]	HU M M, HU T, LI Z J , et al.Surface functional groups and interlayer water determine the electrochemical capacitance of Ti₃C₂T_x MXene.ACS Nano, 2018,12(4):3578-3586. DOI URL PMID
[35]	ZHU Y W, MURALI S, STOLLER M D , et al.Carbon-based supercapacitors produced by activation of graphene.Science, 2011,332(6037):1537-1541. DOI URL
[36]	HU T, LI Z J, HU M M , et al.Chemical origin of termination- functionalized MXenes: Ti₃C₂T₂ as a case study.Journal of Physical Chemistry C, 2017,121(35):19254-19261. DOI URL PMID
[37]	YAN J, REN C E, MALESKI K , et al.Flexible MXene/graphene films for ultrafast supercapacitors with outstanding volumetric capacitance. Advanced Functional Materials, 2017,27(30):1701264. DOI URL
[38]	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.Advanced Energy Materials, 2015,5(15):1500589 DOI URL
[39]	HU L B, PASTA M, LA MANTIA F , et al.Stretchable, porous, and conductive energy textiles.Nano Letters, 2010,10(2):708-714. DOI URL PMID
[40]	PASTA M, LA MANTIA F, HU L B , et al.Aqueous supercapacitors on conductive cotton. Nano Research, 2010,3(6):452-458. DOI URL
[41]	WANG Y S, LI S M, HSIAO S T , et al.Integration of tailored reduced graphene oxide nanosheets and electrospun polyamide-66 nanofabrics for a flexible supercapacitor with high-volume- and high-area-specific capacitance. Carbon, 2014,73:87-98. DOI URL
[42]	ZHOU Q L, YE X K, WAN Z Q , et al.A three-dimensionalflexible supercapacitor with enhancedperformance based on lightweight, conductive graphene-cotton fabricelectrode.Journal of Power Sources, 2015,296:186-196. DOI URL
[43]	YOO J E, BAE J . High-performance fabric-based supercapacitors using water-dispersible polyaniline-poly(2-acrylamido-2-methyl- 1-propanesulfonic acid). Macromolecular Research, 2015,23(8):749-754. DOI URL
[44]	JOST K, PEREZ C R, MCDONOUGH J K , et al.Carbon coated textiles for flexible energy storage.Energy & Environmental Science, 2011,4(12):5060-5067. DOI URL PMID
[45]	KURRA N, AHMED B, GOGOTSI Y , et al.MXene-on-paper coplanar microsupercapacitors..Advanced Energy Materials, 2016,6(24):1600969. DOI URL
[46]	FRACKOWIAK E, DELPEUX S, JUREWICZ K , et al.Enhanced capacitance of carbon nanotubes through chemical activation.Chemical Physics Letters, 2002,361(1/2):35-41. DOI URL PMID
[47]	DU X, ZHAO W, WANG Y , et al.Preparation of activated carbon hollow fibers from ramie at low temperature for electric double-layer capacitor applications. Bioresource Technology, 2013,149:31-37. DOI URL
[48]	WANG Y, SHI Z, HUANG Y , et al.Supercapacitor devices based on graphene materials. The Journal of Physical Chemistry C, 2009,113(30):13103-13107. DOI URL PMID
[49]	WANG P, ZHAO Y J, WEN L X ,et al. Ultrasound-microwave- assisted synthesis of MnO₂ supercapacitor electrode materials.Industrial & Engineering Chemistry Research, 2014,53(52):20116-20123. DOI URL PMID
[50]	ZHENG J P, CYGAN P J, JOW T R . Hydrous ruthenium oxide as an electrode material for electrochemical capacitors. Journal of the Electrochemical Society, 1995,142(8):2699-2703. DOI URL PMID
[51]	SNOOK G A, KAO P, BEST A S . Conducting-polymer-based supercapacitor devices and electrodes. Journal of Power Sources, 2011,196(1):1-12. DOI URL