MXene复合气凝胶在电化学储能领域的研究进展

李思琦; 史纳蔓; 卢道坤; 干露露; 张如全; 罗磊

doi:10.13801/j.cnki.fhclxb.20230731.003

MXene复合气凝胶在电化学储能领域的研究进展

doi: 10.13801/j.cnki.fhclxb.20230731.003

李思琦¹,
史纳蔓¹,
卢道坤¹,
干露露¹,
张如全¹,
罗磊^{1, 2, ,}

1.
武汉纺织大学　纺织科学与工程学院，武汉 430200
2.
武汉纺织大学　纺织新材料与先进加工技术国家重点实验室，武汉 430200

基金项目: 湖北省重点研发计划项目(2020DGC003)；湖北省自然科学基金项目(2021CFB478)；武汉纺织大学大学生创新训练项目(S202310495013)

详细信息

通讯作者:
罗磊，博士，副教授，硕士生导师，研究方向为功能纤维材料　E-mail: leiluo@wtu.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-05-08
- 修回日期: 2023-07-06
- 录用日期: 2023-07-23
- 网络出版日期: 2023-07-31
- 刊出日期: 2024-01-01

Research progress of MXene composite aerogels in the field of electrochemical energy storage

LI Siqi¹,
SHI Naman¹,
LU Daokun¹,
GAN Lulu¹,
ZHANG Ruquan¹,
LUO Lei^{1, 2
, ,}

1.
School of Textile Science and Engineering, Wuhan Textile University, Wuhan 430200, China
2.
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, China

Funds: Key R&D Program Projects of Hubei Province (2020DGC003); Natural Science Fundation of Hubei Province (2021CFB478); Innovation Training Program for College Students of Wuhan Textile University (S202310495013)

摘要

摘要: MXene材料目前已在电磁屏蔽、传感、污水处理等多个领域具有广泛应用，其优异的电化学性能使得其在储能领域也展现出广阔的应用前景。然而，MXene的自堆叠与易氧化等特性，限制了其进一步发展。将MXene组装成三维(3D)结构复合材料是解决上述问题的有效途径之一。3D多孔结构能为离子传输/存储提供更多通道和活性位点，可有效提高电化学性能。本文主要回顾MXene复合气凝胶的最新研究进展，详细阐述MXene复合气凝胶的制备方法以及其在电池、超级电容器等储能方面的应用。最后，对其发展方向进行了展望。
- MXene /
- 气凝胶 /
- 复合材料 /
- 制备工艺 /
- 电化学储能 /
- 电池 /
- 超级电容器
Abstract: MXene materials have been widely used in many fields, such as electromagnetic shielding, sensing, and wastewater treatment. The excellent electrochemical properties of MXene makes it demonstrate broad application prospects in the field of energy storage as well. However, the self-stacking and easy oxidation characteristics of MXene limit its further development. The assembly of MXene into three-dimensional (3D) structural composites is one of the effective way to solve the above problems. The 3D porous structure can provide more channels and active sites for ion transport or storage, which can effectively improve the electrochemical performance. This article reviews the recent researches of MXene composite aerogels. The preparation methods and applications of MXene composite aerogels in energy storage, such as batteries and supercapacitors, are discussed in detail. Finally, the prospects for its future development direction were also presented.
- MXene /
- aerogel /
- composites /
- preparation processes /
- electrochemical energy storage /
- batteries /
- supercapacitors

HTML全文

图 1 (a) 超轻多孔TiVC/还原氧化石墨烯(rGO)双金属气凝胶(TVGA)的合成及Li-CO₂电池原理图(I)、TVGA气凝胶光学图(II)和具有良好柔韧性的TVGA阴极片的光学图(III)^[24]；(b) 制造Ti₃C₂T_x MXene-石墨烯复合气凝胶(MGA)材料的示意图(I)和在无约束条件下MGA材料的顶部(左)和侧视图的SEM图像(II)^[27]；(c) Mo-Ti/MXene (Mx)-rGO-纤维素纳米纤维(GN)气凝胶(Mo-Ti/Mx-GN)合成工艺示意图(I)和SEM图像(II)^[29]；(d) 3D多孔1T MoS₂/Ti₃C₂T_x复合气凝胶 X-Z和X-Y横截面SEM图像^[30]；(e) 3D打印V₂CT_x/rGO-碳纳米管(CNT)微栅气凝胶电极的制备过程示意图(I)和30%V₂CT_x/rGO-CNT微格栅气凝胶的SEM图像(II)^[40]；(f) 3D打印各种结构的模板^[41]；(g) Ti₃C₂T_x/碳纳米纤维(CNF)复合气凝胶制备工艺示意图(I)和Ti₃C₂T_x/CNF6-2的SEM图像(II)^[43]；(h) 具有褶皱结构的MXene平台器件(上)和Mg²⁺-MXene气凝胶的SEM图像(下)^[45]

Figure 1. (a) Synthesis of ultralight porous TiVC/reduced graphene oxide (rGO) aerogels (TVGA) and schematic diagram of Li-CO₂ battery (I), optical photos of block TVGA (II) and TVGA cathode sheet with good flexibility (III)^[24]; (b) Schematic illustration of fabricating Ti₃C₂T_x MXene and graphene aerogel (MGA) material (I), SEM images of top (left) and side views under unconstrained conditions for the MGA material (II)^[27]; (c) Schematic diagram illustrating the synthesis process (I) and SEM images (II) of the metallic 1T MoS₂ and rich oxygen vacancies Ti_nO_2n–1/MXene hierarchical bifunctional catalyst (Mo-Ti/Mx) anchored on a rGO-cellulose nanofiber (GN) host (Mo-Ti/Mx-GN) aerogel^[29]; (d) X-Z and X-Y cross-sectional SEM images of 3D highly-porous 1T MoS₂/Ti₃C₂T_x composite aerogel^[30]; (e) Schematic diagram of the preparation process of a 3D-printed V₂CT_x/rGO-carbon nanotube (CNT) microgrid aerogel electrode (I), SEM image of the 30%V₂CT_x/rGO-CNT microgrid aerogel (II)^[40]; (f) 3D printing templates for various structures^[41]; (g) Schematic illustration of the fabrication process of Ti₃C₂T_x/carbon nanofiber (CNF) composite aerogel (I), SEM image of Ti₃C₂T_x/CNF6-2 (Ⅱ)^[43]; (h) MXene platform device with folded structure (top), SEM image of a Mg²⁺-MXene aerogel (bottom)^[45]

GO—Graphene oxide; ΔT—Temperature

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图 2 (a) 氧化石墨烯(GO)辅助组装Ti₃C₂T_x MXene复合气凝胶经硫改性(SMGA)后的SEM图像^[48]；(b) SMGA电极在0.1~3 mV·s⁻¹不同扫描速下的CV曲线^[48]；(c) 组装活性炭(AC)//SMGA SiC供电LED阵列和电子温度计的数码照片^[48]；(d) 锑单原子和量子点(~5 nm)共修饰Ti₃C₂T_x MXene气凝胶(Sb SQ@MA)的SEM图像^[50]；(e) Sb SQ@MA与钾离子电池(PIBs)中其他报道的Sb基阳极的倍率性能比较^[50]；(f) Sb SQ@MA长期循环性能^[50]

Figure 2. (a) SEM image of graphene oxide (GO)-assisted assembly of Ti₃C₂T_x MXene aerogel after sulfur modified (SMGA)^[48]; (b) CV curves of the SMGA electrode at different scan rates from 0.1-3 mV·s⁻¹^[48]; (c) Digital photos of LED arrays and electronic thermometer powered by the assembled activated carbon (AC)//SMGA SiC^[48]; (d) SEM image of antimony single atoms and quantum dots (~5 nm) codecorated Ti₃C₂T_x MXene-based aerogels (Sb SQ@MA)^[50]; (e) Comparison of the rate performance of the Sb SQ@MA with other reported Sb-based anodes in potassium-ion batteries (PIBs)^[50]; (f) Long-term cycling performance of the Sb SQ@MA^[50]

NC—N-doped three-dimensional porous carbon

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图 3 (a) MXene涂层三维气凝胶(MCG-6)复合气凝胶在不同放大倍数的SEM图像^[55]；(b) MCG-6复合气凝胶电极提高锂硫电池动力学反应速率的示意图^[55]；(c) MCG-6电极在各种速率下的恒流充放电曲线^[55]；(d) MXene/C-CNF复合气凝胶(MC-6)的SEM图像^[57]；(e) MC-6复合气凝胶电极在不同速率下的恒流充放电曲线^[57]；(f) MXene/T-CNF复合气凝胶(MT-4)的SEM图像^[57]；(g) MT-4复合气凝胶电极在不同速率下的恒流充放电曲线^[57]；(h) 层状(PA) MXene-CNT-50复合气凝胶的SEM图：(I) 俯视图(插图是PA MXene/CNT-50整体的照片)；(II) 侧视图； (III) 高放大率图^[54]

Figure 3. (a) SEM images of MXene-coated three-dimensional aerogel (MCG-6) composite aerogel under different magnifications^[55]; (b) Illustration of MCG-6 composite aerogel electrode enhancing the kinetic reaction rate of lithium-sulfur battery^[55]; (c) Galvanostatic charge and discharge curves of MCG-6 electrodes at various rates^[55]; (d) SEM image of MXene/C-CNF composite aerogel (MC-6)^[57]; (e) Galvanostatic charge and discharge curves of MC-6 composite aerogel electrode at various rates^[57]; (f) SEM image of MXene/T-CNF composite aerogel (MT-4)^[57]; (g) Galvanostatic charge and discharge curves of MT-4 composite aerogel electrode at various rates^[57]; (h) SEM images of the parallel-aligned (PA)-MXene/CNT-50 composite aerogel: (I) Top-view (Inset is a photo of the PA-MXene/CNT-50 monolith); (II) Side-view; (III) High magnification^[54]

T-CNF—TEMPO-oxidized cellulose nanofibers; C-CNF—Cation-CNF; TEMPO—2, 2, 6, 6-tetramethylpiperidoxyl

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图 4 (a) 两个混合超级电容器(HSC)器件串联，为温度计供电超过8 min^[32]；(b) (I)自愈机制示意图和光学图；(II) 自愈后的聚氨酯(PU)展示：弯曲状态(左上)，平坦状态(左下)，支撑500 g质量(右)，矩形表示伤口/愈合的位置；(III) MXene/rGO 复合气凝胶的SEM图像^[60]；(c) (I) MLSG-6复合气凝胶的SEM图像；(II) 显示LSG//MLSG-6不对称装置与其他最新超级电容器相比的面积能量和功率密度的Ragone图；(III) 由一个LSG//MLSG-6不对称超级电容器供电的小灯泡^[61]

Figure 4. (a) Two hybrid supercapacitor (HSC) devices connected in series to power a thermometer more than 8 min^[32]; (b) (I) Schematic diagrams and optical images of the self-healable mechanism; (II) Demonstration of after self-healing polyurethane (PU): Under bending state (top left), under flat state (bottom left), supporting a 500 g mass (right) (Rectangles indicate the wound/healing positions); (III) SEM image of MXene/rGO composite aerogel^[60]; (c) (I) SEM images of MLSG-6 composite aerogel; (II) Ragone plot displaying areal energy and power densities of LSG//MLSG-6 asymmetric device in comparison to the other state-of-the-art supercapacitors; (III) A small bulb powered by one LSG//MLSG-6 asymmetric supercapacitor^[61]

PANI—Polyaniline; ESCNF—Electrospinning carbon nanofiber; PEDOT—Poly(3, 4-ethylenedioxythiophene); PSS—Polystyrene sulfonate; MLSG—Lignosulfonate (LS) modified-MXene (Ti₃C₂T_x)-reduced graphene oxide; LSG—LS-functionalized reduced graphene oxide; CDC—Carbide-derived carbons

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图 5 (a) LiMn₂O₄ (LMO)//Ti₃C₂T_x MXene-石墨烯复合气凝胶(MGA)@Zn软包电池在不同折叠状态下的循环性能^[27]；(b) 分别在10、30、50次循环时软包电池的容量曲线^[27]

Figure 5. (a) Cycling performance of the LiMn₂O₄ (LMO)//Ti₃C₂T_x MXene and graphene aerogel (MGA)@Zn pouch cells at various folding times^[27]; (b) Capacity profiles of the pouch cells at 10, 30, 50 cycles, respectively^[27]

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表 1 MXene复合气凝胶超级电容器电化学性能

Table 1. Electrochemical properties of supercapacitors assembled by MXene composite aerogels

Materials	Key assembly method	Electrochemical performance	Ref.
Ti₃C₂T_x/cellulose nanocrystal	Waterborne polyurethane (WPU) crosslinking	Cycling stability: 86.7%, 4000 cycles; Energy density: 38.5 μW·h·cm⁻² at power density of 1375 μW·cm⁻²	[62]
Ti₃C₂T_x	Urea-assisted hydrothermal process for nitrogen doping	Cycling stability: 85%, 5000 cycles; Energy density: 21.7 W·h·kg⁻¹ at a power density of 600 W·kg⁻¹	[63]
Ti₃C₂T_x/rGO	Ascorbic acid reduction	Specific capacitance: ~65 F·g⁻¹ at 0.5 A·g⁻¹; Cycling stability: 94.5%, 10000 cycles; Energy density: 3.81 W·h·kg⁻¹ at a power density of 163 W·kg⁻¹	[64]
Ti₃C₂T_x/rGO/MnO₂	Ascorbic acid reduction	Cycling stability: 90.5%, 5000 cycles; Energy density: 50.1 W·h·kg⁻¹ at a power density of 2.1 kW·kg⁻¹	[65]
Ti₃C₂T_x/CoS	Melamine foam loading	Specific capacitance: 41.5 F·g⁻¹ at 0.2 A·g⁻¹; Cycling stability: 80.39%, 5000 cycles; Energy density: 10.66 W·h·kg⁻¹ at a power density of 135.96 W·kg⁻¹	[66]
Ti₃C₂T_x/rGO/Co₃O₄	Hydrazine hydrate reduction	Specific capacitance: 345 F·g⁻¹ at 1 A·g⁻¹; Cycling stability: 85%, 10000 cycles; Energy density: 8.25 W·h·kg⁻¹ at a power density of 159.94 W·kg⁻¹	[67]
Ti₃C₂/rGO	Zn foil reduction	Specific capacitance: 41 mF·cm⁻², 1 mA·cm⁻²; Cycling stability: Almost no capacitance decay, 1000 cycles; Energy density: ~2.1 μW·h·cm⁻² at a power density of ~301.2 μW·cm⁻²	[68]
MXene/zeolitic imida- zolate framework-8 (ZIF-8)	Metal-organic frameworks deposition	Specific capacitance: 1176 F·g⁻¹ at 0.5 A·g⁻¹; Cycling stability: 90.88%, 10000 cycles; Energy density: 57.84 W·h·kg⁻¹ at a power density of 628 W·kg⁻¹	[69]
Ti₃C₂T_x/rGO	Ascorbic acid reduction	Cycling stability: 80%, 4000 cycles; Energy density: 7.5 W·h·kg⁻¹ at a power density of 500 W·kg⁻¹	[70]
Ti₃C₂T_x/rGO/Fe₃O₄	Ethylenediamine (EDA) crosslinking	Specific capacitance: 365 mF·cm⁻², 1 mA·cm⁻²; Cycling stability: 84.5%, 30000 cycles; Energy density: 130 μW·h·cm⁻² at a power density of 802 μW·cm⁻²	[71]
Ti₃C₂T_x/rGO/NiCo₂O₄	Ascorbic acid reduction	Specific capacitance: 87 F·g⁻¹ at 1 A·g⁻¹; Energy density: 40.5 W·h·kg⁻¹ at the power density of 1125.1 W·kg⁻¹	[72]
Ti₃C₂T_x/CNT	Ice template method	Specific capacitance: 410.7 mF·cm⁻², 0.8 mA·cm⁻²; Cycling stability: 91.2%, 5000 cycles	[73]
Polypyrrole (PPy)@poly- vinyl alcohol (PVA)/ bacterial cellulose (BC)/Ti₃C₂T_x	Ice template method	Specific capacitance: 3948 mF·cm⁻², 0.47 mA·cm⁻²; Cycling stability: 120%, 10000 cycles; Energy density: 178 μW·h·cm⁻² at a power density of 951 μW·cm⁻²	[74]
Ti₃C₂T_x/sodium alginate (SA)	Ice template method	Specific capacitance: 284.5 F·g⁻¹, 2 mV·s⁻¹; Cycling stability: Almost no capacitance decay, 20000 cycles	[36]

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