MXene基纳米材料在高性能水系锌离子混合电容器中的研究进展

ZHANG Ming-hui; XU Wen; WU Li-sha; DONG Yan-feng

doi:10.1016/S1872-5805(22)60611-5

MXene基纳米材料在高性能水系锌离子混合电容器中的研究进展

doi: 10.1016/S1872-5805(22)60611-5

张明慧¹,
徐文¹,
武丽莎¹,
董琰峰^{1, 2, ,}

1.
东北大学理学院化学系，辽宁沈阳 110819
2.
中国科学院山西煤炭化学研究所炭材料重点实验室，山西太原 030001

基金项目: 辽宁省“兴辽英才计划”青年拔尖人才(XLYC2007129); 辽宁省自然科学基金(2020-MS-095)；中央高校基本科研业务费(N2105008)；中国科学院炭材料重点实验室开放课题(KLCMKFJJ2004)

详细信息

通讯作者:
董琰峰，副教授. E-mail：dongyanfeng@mail.neu.edu.cn

中图分类号: TB33
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出版历程
- 收稿日期: 2022-03-02
- 修回日期: 2022-04-19
- 网络出版日期: 2022-04-27
- 刊出日期: 2022-06-01

Recent progress in MXene-based nanomaterials for high-performance aqueous zinc-ion hybrid capacitors

1.
Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China
2.
CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: This work was financially supported by LiaoNing Revitalization Talents Program (XLYC2007129), the Natural Science Foundation of Liaoning Province (2020-MS-095), the Fundamental Research Funds for the Central Universities of China (N2105008), and the CAS Key Laboratory of Carbon Materials (KLCMKFJJ2004)

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Author Bio:
^†张明慧、徐文为共同第一作者

Corresponding author: DONG Yan-feng, Associate Professor. E-mail: dongyanfeng@mail.neu.edu.cn

摘要

摘要: 水系锌离子混合电容器（ZHCs）具有本征安全、低成本的优点，在大规模储能领域中具有广阔的应用前景。然而，传统的多孔炭正极具有不理想的孔结构，难以实现有效的锌离子的存储和扩散，此外锌箔负易遭受枝晶和副反应，因此传统ZHCs常表现出较低的能量密度和较短的循环寿命，严重制约其实际应用。二维过渡金属碳/氮化物（MXene）具有高导电基体和丰富表面官能团，为构筑ZHCs用高容量正极和长循环锌负极提供了新机遇。本文系统总结了高性能ZHCs用MXene基纳米材料的最新进展，先简要介绍了ZHCs的基础知识如工作原理和关键电化学参数，随后详细阐述了高性能ZHCs用MXene基正极（纯MXene、插层MXene、掺杂MXene、MXene基杂化材料（MXene/金属硫化物、MXene/炭、MXene/聚合物））和负极的研究进展，最后简要讨论了MXene基纳米材料在下一代ZHCs应用中的挑战和展望。
- 锌离子混合电容器 /
- MXene /
- 正极 /
- 负极
Abstract: Aqueous zinc-ion hybrid capacitors (ZHCs) have an intrinsic safety and low cost, and are promising for use in large-scale energy storage devices. However, traditional porous carbon cathodes have inappropriate pore structures for zinc ion storage and diffusion. Moreover, zinc foil anodes suffer from the growth of Zn dendrites and side reactions, so that traditional ZHCs usually have a non-competitive energy density and unsatisfactory service life, seriously inhibiting their practical use. Two-dimensional transition metal carbide/nitride MXenes with a highly conductive matrix and abundant surface functional groups are good choices for constructing high-capacity cathodes and long-life Zn anodes for high-performance ZHCs. Recent progress in MXene-based nanomaterials as electrode materials of advanced ZHCs is summarized. The fundamentals of ZHCs are first introduced, such as working principles and key electrochemical parameters. The use of various MXene-based cathodes and anodes in high-performance aqueous ZHCs are then considered and, finally, the challenges and prospects for MXene-based nanomaterials for next-generation ZHCs are briefly discussed.
- Zinc-ion hybrid capacitors /
- MXene /
- Cathodes /
- Anodes

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FIG. 1535. FIG. 1535.

FIG. 1535..

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Figure 1. Main progress of MXene-based nanomaterials for ZHCs. (a) MXene was firstly obtained by selective etching of Al in Ti₃AlC₂ with HF acid^[42] (Reprinted with permission by copyright 2011, Wiley). (b) MXene-reduced graphene oxide aerogels as the cathode^[32](Reprinted with permission by copyright 2019, Wiley). (c) Sn⁴⁺ pre-embedded MXene cathode^[33] (Reprinted with permission by copyright 2020, Wiley). (d) Nitrogen-doped MXene-based heterostructure cathode^[34] (Reprinted with permission by copyright 2021, RSC). (e) Nanofibrillated cellulose adhered Ti₃C₂T_x flake cathode^[35](Reprinted with permission by copyright 2022, Elsevier). (f) Zn nanosheets vertically deposited on Ti₃C₂ MXene^[36] (Reprinted with permission by copyright 2019, ACS). (g) Ti₃C₂T_x MXene paper host for Zn ^[37] (Reprinted with permission by copyright 2021, ACS). (h) Heterolayer of MXene and ZnS on Zn^[38] (Reprinted with permission by copyright 2021, ACS). (i) Ti₃C₂T_x MXene wrapped Zn powder^[39] (Reprinted with permission by copyright 2021, ACS).

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Figure 2. Schematic diagram of the applications of MXene based nanomaterials for aqueous zinc-ion hybrid capacitors.

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Figure 3. Schematic of the storage mechanisms of (a) electric double layer capacitance, (b) redox pseudocapacitance, and (c) intercalation pseudocapacitance^[44](Reprinted with permission by copyright 2021, Wiley). (d-e) Schematic diagrams of energy storage mechanisms of (d) the first type and (e) the second type ZHCs.

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Figure 4. (a) Schematic diagram of 3DP MXene electrodes. (b) SEM image of 3DP MXene. (c) Specific capacitances based on mass and area at different current densities^[62](Reprinted with permission by copyright 2021, ACS). (d) Schematic diagram of the preparation process of diamine-intercalated MXene. (e) SEM image of PDA-MXene. (f) Specific capacitances of MXene electrodes intercalated with different diamine molecules at different current densities. (g) Cycling performance of PDA-MXene electrodes at 1 A g^−1[64](Reprinted with permission by copyright 2021, Wiley).

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Figure 5. (a) Schematic diagram of preparation of Ti₃C₂T_x/BiCuS_2.5. (b) Ragone plot of Ti₃C₂T_x/BiCuS_2.5 and other reported electrodes. (c) Cycling performance of Ti₃C₂T_x/BiCuS_2.5 electrodes at a current density of 20 A g^−1[67](Reprinted with permission by copyright 2021, Elsevier).

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Figure 6. (a) Schematic of the synthesis of V₂C@CNTs. (b) SEM image of V₂C@CNTs^[68](Reprinted with permission by copyright 2019, Wiley). (c) SEM image of MXene-rGO^[32] (Reprinted with permission by copyright 2019, Wiley). (d) Schematic of the synthesis of NMXC^[34] （Reprinted with permission by copyright 2021, RSC）.

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Figure 7. (a) Schematic diagram of the preparation of a flexible layered Ti₃C₂T_x MXene@Zn paper. (b) Coulombic efficiency of Zn plating/stripping of Zn|Ti@Zn batteries and Zn|MXene@Zn batteries at an areal capacity of 1 mAh cm⁻² and a current density of 1 mA cm^−2[37](Reprinted with permission by copyright 2021, ACS). (c) Cycling performance of Zn//Ti₃C₂I₂ and MCl-Zn//Ti₃C₂I₂ batteries at a current density of 3 A g⁻¹^[82]. (Reprinted with permission by copyright 2022, ACS).

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Figure 8. (a) Schematic of the synthesis of S/MX@ZnS@Zn. (b) Cycling performance of pristine Zn and S/MX@ZnS@Zn anodes at a rate of 0.5 mA cm⁻² and an areal capacity of 0.5 mAh cm⁻². SEM images of (c) pristine Zn anodes and S/MX@ZnS@Zn-350 anodes after 10 and 100 cycles^[38] (Reprinted with permission by copyright 2021, ACS). (d) SEM image of MXene@Zn. (e) Nucleation overpotential of Zn-p and MXene@Zn at 1mA cm⁻². (f) Long-cycle performance diagram of Zn-p and MXene@Zn symmetric batteries at 1 mA cm^−2[39](Reprinted with permission by copyright 2021, ACS).

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Table 1. A summary of various reported MXene based cathodes for ZHCs.

Type of cathode	Sample	Voltage (V)	Electrolyte	Capacity	Capacity retention	Energy density	Power density	Ref.
MXenes	Ti₃C₂T_x	0.05-1.35	2 M ZnSO₄	132 F g⁻¹ at 0.5 A g⁻¹	82.5% after 1000 cycles	−	−	[36]
	Mo_1.33CT_z-Ti₃C₂T_z	0.01-1.3	3 M Zn(CF₃SO₃)₂	115 mAh g⁻¹ at 1 A g⁻¹	90% after 8000 cycles	103 Wh kg⁻¹	0.143 KW kg⁻¹	[60]
	3D-PHMF	0-1.3	2 M Zn(CF₃SO₃)₂	105.6 mAh g⁻¹ at 0.2 A g⁻¹	90% after 20000 cycles	53.6 Wh kg⁻¹	104.5W kg⁻¹	[61]
	3DP MXene	0.1-1.2	2 M ZnSO₄	259.7 F g⁻¹ at 0.1 A g⁻¹	86.5% over 6000 cycles	0.10 mWh cm⁻²	5.90 mW cm⁻²	[62]
	Ti₃C₂T_x (Fiber- shaped ZHCs )	0-1.2	1.5 M ZnSO₄	214 mF cm⁻² at 5 mV s⁻¹	83.58% after 5000 cycles	42.8 μWh cm⁻²	0.64 mW cm⁻²	[63]
Intercalated MXenes	PDA-MXene	0.2-1.1	2 M ZnSO₄	124.4 F g⁻¹ at 0.2 A g⁻¹	85% after 10000 cycles	13.8 Wh kg⁻¹	4500 W kg⁻¹	[64]
	In-situ pillared Ti₃C₂	0.2-1.2	0.1 M ZnSO₄	73 mAh g⁻¹ at 0.2 A g⁻¹	96% after 1000 cycles	−	−	[65]
	Sn⁴⁺-Ti₂CT_x/C	0.1-2.0	2 M ZnSO₄	138 mAh g⁻¹ at 0.1 A g⁻¹	>96% after 12500 cycles	−	−	[33]
Heteroatom-doped MXenes	N-Ti₃C₂	0.05-1.2	1 M ZnSO₄	247.9 F g⁻¹ at 0.1 A g⁻¹	88.34% after 6000 cycles	45.54 Wh kg⁻¹	4093 W kg⁻¹	[66]
MXene/metal sulfide hybrids	Ti₃C₂T_x/ Bi₂S₃@N-C	0-1.4	ZnSO₄	653 F g⁻¹ at 1 A g⁻¹	85.7% after 2000 cycles	46.98 Wh kg⁻¹	750 W kg⁻¹	[51]
	Ti₃C₂T_x/BiCuS_2.5	0-0.8	1 M ZnSO₄	840 C g⁻¹ at 1 A g⁻¹	82% after 10000 cycles	298.4 Wh kg⁻¹	7200 W kg⁻¹	[67]
MXene/carbon hybrids	V₂C/CNTs	0.1-1.1	1 M ZnSO₄	90.2 F g⁻¹ at 10 A g⁻¹	−	−	−	[68]
	MXene-rGO	0.2-1.6	2 M ZnSO₄	128.6 F g⁻¹ at 0.4 A g⁻¹	95% after 75000 cycles	34.9 Wh kg⁻¹	279.9 W kg⁻¹	[32]
	NMXC	0.2-1.8	2 M ZnSO₄	83.9 mAh g⁻¹ at 0.1 A g⁻¹	96.4 % after 10000 cycles	64.5 Wh kg⁻¹	3.9 kW kg⁻¹	[34]
MXene/polymer hybrids	MN-80	−	2 M ZnSO₄	92.1 mAh g⁻¹ at 0.5 mA cm⁻²	94.31% after 10000 cycles	−	−	[35]
	MXene/BCF	0-1.2	2 M Zn(CF₃SO₃)₂ /PAM gel	178.6 mF cm⁻² at 0.5 mA cm⁻²	72.3% after 3000 cycles	34.0 μWh cm⁻²	−	[69]
	MXene/BC@PPy	0-1.9	2 M Zn(CF₃SO₃)₂-0.1 M MnSO₄/PAM hydrogel	388 mF cm⁻² at 1 mA cm⁻²	95.8% after 25000 cycles	145.4 μWh cm⁻²	3.78 mW cm⁻²	[70]
Note: M: mol L⁻¹

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Table 2. A summary of various reported MXene-based anodes for ZHCs.

Role of MXenes	Anode name	Voltage hysteresis	Nucleation overpotential	Life span	Coulombic efficiency	Ref.
Zn host materials	Ti₃C₂T_x MXene@Zn	75 mV (1 mA cm⁻²)	83 mV	300 h (1 mA cm⁻²)	94.13% at 5 mA cm⁻² (400 cycles)	[37]
	MCl-Zn	103 mV (10 mA cm⁻²)	40.7 mV (1 mA cm⁻²)	840 h (2 mA cm⁻²)	99.50% at 1 mA cm⁻² (50 cycles)	[82]
	MGA@Zn	64 mV (10 mA cm⁻²)	−	1050 h (10 mA cm⁻²)	≈99.67% at 10 mA cm⁻² (600 cycles)	[83]
Protecting layers	S/MX@ZnS@Zn-350	0.03 V (0.5 mA cm⁻²)	−	1600 h (10 mA cm⁻²)	−	[38]
	MXene-mPPy/Zn	22 mV (0.2 mA cm⁻²)	10 mV	2500 h (0.2 mA cm⁻²)	−	[84]
	AMX-Zn	−	−	−	−	[81]
	MXene@Zn (Zn-p)	30 mV (1 mA cm⁻²)	27.4 mV (1 mA cm⁻²)	200 h (1 mA cm⁻²)	−	[31]

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