纳米炭材料应用于稳定锌离子电池中锌负极

GONG Yun; XUE Yu-hua

doi:10.1016/S1872-5805(23)60740-1

纳米炭材料应用于稳定锌离子电池中锌负极

doi: 10.1016/S1872-5805(23)60740-1

贡昀,
薛裕华^,

上海理工大学材料与化学学院，上海 200093

基金项目: 国家自然科学基金(52172095)，上海市地方院校能力建设计划项目(20060502200)，上海市教委科研创新计划重大项目(2019-01-07-00-07-E00015)

详细信息

通讯作者:
薛裕华，教授. E-mail：xueyuhua@usst.edu.cn

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2022-12-18
- 录用日期: 2023-04-13
- 修回日期: 2023-04-13
- 网络出版日期: 2023-05-12
- 刊出日期: 2023-06-01

Carbon nanomaterials for stabilizing zinc anodes in zinc-ion batteries

GONG Yun,
XUE Yu-hua^,

University of Shanghai for Science and Technology, Shanghai 200093, China

Funds: This work was supported financially by the National Natural Science Foundation of China (52172095), the Natural Science Foundation of Shanghai (19ZR1435000), the Science and Technology Commission of Shanghai Municipality (20060502200), the Innovation Program of Shanghai Municipal Education Commission (2019-01-07-00-07-E00015)

More Information

Author Bio:
贡　昀，博士研究生. E-mail：211590181@st.usst.edu.cn

Corresponding author: XUE Yu-hua, Professor. E-mail: xueyuhua@usst.edu.cn

摘要

摘要: 水系锌离子电池（ZIBs）由于价格低、安全性好、储能性能优异等优点，在电网和可穿戴设备中具有极大的前景。然而，锌离子电池的锌金属负极并不稳定，例如，锌负极上会形成锌枝晶，同时还会发生析氢反应和其他副反应。这些不稳定的因素阻碍了ZIBs的应用。最近，纳米炭材料因其独特的结构、优异的导电性和良好的稳定性成为优化锌负极的重要材料。这篇综述系统地概述了纳米炭材料用于稳定ZIBs中锌负极的最新进展。总结了纳米炭材料稳定锌负极的4种策略，包括使用炭材料作为基底、保护涂层、电解质添加剂和隔膜改性。最后，指出了纳米炭材料在稳定锌负极方面的挑战和前景。
- 锌负极 /
- 纳米炭材料 /
- 石墨烯 /
- 纳米碳管 /
- 抑制锌枝晶
Abstract: Because of their low price, excellent safety and energy storage performance, aqueous zinc-ion batteries (ZIBs) have great potential for use in the power grid and in wearable devices. However, the Zn anode of ZIBs is not stable, for example, Zn dendrite can be formed on the Zn anode accompanied by hydrogen evolution and side reactions, leading to its instability, which has been an obstacle to its use. Carbon nanomaterials have recently been used to improve the performance of Zn anodes due to their unique structure, excellent conductivity and good stability. This review summarizes this recent development for stabilizing zinc anodes. The carbon nanomaterials are used are as hosts, protective coating layers, electrolyte additives and modifiers in the separators to stabilize the Zn electrodes. The problems involved in doing this are presented, and some future developments are outlined.
- Zinc anode /
- Carbon nanomaterials /
- Graphene /
- Carbon nanotubes /
- Zinc dendrite

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FIG. 2359. FIG. 2359.

FIG. 2359.. FIG. 2359.

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Figure 1. (a) Number of publications on carbon nanomaterials for stabilizing zinc anode, which was indexed by two topic keywords of ‘‘zinc anode’’ and ‘‘carbon’’ from the Web of Science. (b) Main progress of carbon nanomaterials as hosts, protecting layers, separators and electrolyte additives in aqueous ZIBs

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Figure 2. Schematic illustration of zinc dendrites, HER, corrosion and passivation

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Figure 3. SEM images of (a) bare CNT and (b) Zn/CNT. (c) The cycling performance of symmetrical batteries based on Zn/CC and Zn/CNT anodes at 2 mA cm⁻²^[35]. (d) The fabrication process of anode using zinc/MWCNTs nanoflakes^[37]. Reprinted with permission

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Figure 4. (a) Scheme illustrating zinc metal crystals grown on a stainless steel substrate and a graphene coated stainless steel substrate. Scanning electron microscopy (SEM) images of Zn electrodeposition on (b) bare stainless steel and (c) graphene-coated stainless steel^[16]. (d) The schematic illustrations of Zn deposition processes on CC and N-VG@CC electrodes. Models of the electric field distributions for (e) Zn@CC electrode and (f) Zn@N-VG@CC electrode after Zn nuclei formation^[15]. Reprinted with permission

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Figure 5. (a) SEM images of Zn anodes at areal capacities from 1 mAh cm⁻² to 10 mAh cm⁻². Scale bars, 2 mm. (b) Schematics of the Zn metal plating process on Zn@ZIF-8-500 anode^[53]. (c) Schematics of the preparing process of the 3D-ZGC host. (d) The optical microscopy images of the Zn plating behavior on bare Zn foil and Zn@3D-ZGC anodes before and after 100 numbers of depositing/stripping cycles. (e) The cycling stability of the whole symmetrical batteries composited of the bare Zn foil (green line) and the Zn@3D-ZGC composite (read line) anodes at 10 mA cm⁻² with a fixed capacity of 1 mAh cm⁻²^[40]. Reprinted with permission

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Figure 6. Schematic illustration of depositing/plating processes of (a) Zn foil electrodes and (b) CNT-stabilized Zn electrodes. SEM images of the carbon nanotubes covered Zn electrode (c) before, and (d) after cycling^[65]. (e-j) The stabilized structures and the optimized configurations of Zn planes and CNTs adsorbing O and S. (k) The long-term cycling stability of a Mn²⁺/Zn²⁺ whole battery^[66]. Reprinted with permission

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Figure 7. (a) Schematics of graphene as a protecting layer on the Zn foil. (b) Schematics of Zn plating process on bare Zn foil (upper image) and NGO@Zn electrode (lower image). (c) SEM images of bare Zn (left) and NGO@Zn (right) electrodes after ten cycles. (d) The linear polarization curves of bare Zn and NGO@Zn electrodes. (e) The long-term stability of the whole pouch batteries of LMO//NGO@Zn and LMO//bare Zn, inset is an optical image of the pouch cell with the NGO@Zn anode and LMO cathode^[18]. Reprinted with permission

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Figure 8. (a) Structure of HsGDY, schematic illustration of HsGDY on Zn plate and digital images of Zn plate before and after HsGDY growth. (b) The cycling stability of Zn@HsGDY//C full cells with different cathodic loading masses^[69]. Reprinted with permission

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Figure 9. (a) Schematics of zinc depositing/plating processes with CG separators^[74]. (b) Schematic illustration of the preparation process of graphene based Janus separator. (c) SEM image of VG carpet on the Janus separator, Scale bar: 1 μm. Inset: High-magnification SEM image of VG, Scale bar: 100 nm^[75]. (d) Schematic illustration of the fabrication process of the Janus separator. (e) Long-term cycling stability of Zn/Zn symmetric cells with the GF separator/Janus separator at 10 mA cm⁻²^[76]. Reprinted with permission

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Figure 10. (a) Schematic illustration of ZIBs with and without GO electrolytes. Cross-section SEM images of the zinc anodes (b) without GO electrolyte additive and (c) with GO electrolyte additive after 200 cycles^[20]. (d) Schematic presentation of the effect of GQD additive for suppressing dendrites growth. SEM images of zinc foil after 20 cycles at 0.8 mA cm⁻² (e) without GQDs and (f) with GQDs^[78]. Reprinted with permission

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Table 1. Performance of recently reported carbon nanomaterials as hosts for Zn anode

Anode	Carbon nanomaterials	Voltage hysteresis	Life span	Coulombic efficiency	Cycling stability	Ref.
Zn/CNT	CNT	27 mV	200 h (2 mA cm⁻²)	97.9% (5 mA cm⁻²)	88.7% (1000 cycles)	[35]
Zn/CNT foam	CNT foam	143 mV	10000 min (3 mA cm⁻²)	—	82.0% (5000 cycles)	[36]
MGA@Zn	Mxene/ graphene	64 mV	1050 h (10 mA cm⁻²)	99.7% (10 mA cm⁻²)	60 cycles	[39]
Zn@N-VG@CC	N-doped vertical graphene	~6 mV	150 h (0.5 mA cm⁻²)	>95.0% (5 mA cm⁻²)	80.0% (300 cycles)	[15]
Zn/GCF	graphene	—	100 h (1mA cm⁻²)	100.0% (0.2 mA cm⁻²)	1000 cycles	[57]
NLSG-Zn	Laser-scribed graphene	18 mV	250 h (1 mA cm⁻²)	99.4% (2 mA cm⁻²)	72.3% (1200 cycles)	[58]
Zn@3D-ZGC	Graphene/carbon nanotube	~50 mV	400 h (10 mA cm⁻²)	—	80.8% (6000 cycles)	[40]
Zn@ZIF-8-500	MOFs derived carbon	—	—	98.6% (2.0 mA cm⁻²)	72.0% (20000 cycles)	[53]
Zn@NOCA@CF	CF	—	240 h (1 mA cm⁻²)	95.7% (1 mA cm⁻²)	200 cycles	[52]
Zn@TiO₂/NC	MOFs derived N-doped carbon	~60 mV	1100 h (5 mA cm⁻²)	99.4% (2.0 mA cm⁻²)	75.0% (1000 cycles)	[59]
Sn@NHCF	N-doped hollow carbon spheres	21 mV	370 h (1 mA cm⁻²)	99.7% (5.0 mA cm⁻²)	2400 cycles	[45]
HSTF	3D hollow SiO₂/TiO₂/CF	122 mV	600 h (10 mA cm⁻²)	99.5% (20.0 mA cm⁻²)	85.0% (10000cycles)	[43]

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Table 2. Performance of carbon nanomaterials as protecting layer for Zn anode

Anode	Carbon nanomaterial	Voltage hysteresis	Life span	Coulombic efficiency	Cycling stability	Ref.
Zn@CNTS	CNTs	36 mV	1800 h (0.1 mA cm⁻²)	—	100% (7000 cycles)	[65]
Zn-CNTs	CNTs	80 mV	600 h (0.5 mA cm⁻²)	—	11000 cycles	[66]
Zn/rGO	RGO	—	300 h (1 mA cm⁻²)	—	88.5% (5000 cycles)	[17]
FLG@Zn	Few-layer graphene	—	500 h (1 mA/cm⁻²)	98.0% (1 mA cm⁻²)	97.0% (5000 cycles)	[72]
Zn/rGO	RGO	170 mV	200 h (10 mA cm⁻²)	—	79.0% (1000 cycles)	[73]
CNG-Zn	Bifunctional cellulose nanowhisker- graphene composite	31 mV	5500 h (0.25 cm⁻²)	99.4% (0.5 mA cm⁻²)	87.8% (5000 cycles)	[67]
NGO@Zn	N-doped graphene oxide	17 mV	1200 h (1 mA cm⁻²)	99.5% (5 mA cm⁻²)	94.0% (300 cycles)	[18]
PEDOT:PSS/GS@Zn	PEDOT:PSS/GS	—	500 h (1 mA cm⁻²)	98.0% (1 mA cm⁻²)	8000 cycles	[68]
Zn@HsGDY	Graphdiyne		2400 h (2 mA cm⁻²)	nearly 100%	50000 cycles	[69]

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