关于水系锌离子电池中无氧钒基正极材料的综述

doi:10.13208/j.electrochem.2219004

摘要/Abstract

摘要：

水系锌离子电池具有功率密度高、环境友好、安全性高、低成本和锌资源丰富等优点，被认为具有潜力成为下一代电化学储能系统。然而，正极材料较差的电化学性能制约了水系锌离子电池的未来发展。尽管氧化锰、氧化钒、普鲁士蓝类似物、有机材料等多种材料已被广泛研究，设计具有高性能的理想正极材料仍面临着巨大挑战。无氧钒基化合物由于具有高的电导率、大的层间距、低的离子扩散势垒和高的理论比容量，受到越来越多的关注。本文总结了无氧钒基化合物的研究进展，包括电极材料的设计、改善其电化学性能的有效途径以及复杂的储能机制，提出了无氧钒基化合物目前面临的挑战和未来的发展前景，为进一步制备新型高性能钒基正极材料提供指导。

关键词: 锌离子电池, 无氧钒基化合物, 储能机制, 电化学性能

Abstract:

Aqueous zinc-ion batteries (AZIBs) are considered as one of the most promising next-generation electrochemical energy storage systems owing to their high-power density, environmental benign, intrinsic safety, and the low cost of the abundant zinc resources. However, their further development is still plagued by the inferior electrochemical performance of cathode materials. Though extensive research has been conducted to investigate various cathode materials (including manganese oxides, vanadium oxides, Prussian blues analogy, and organic materials), design of high-performance cathodes with satisfying capacity and long-term cycling stability still faces great challenges. Oxygen-free vanadium-based compounds, owing to their better conductivity, larger interlayer spacing, lower ion diffusion barrier and higher theoretical specific capacity than those of vanadium oxides, have gained increasing attention recently. In this review, we summarize the recent development about the emerging oxygen-free vanadium-based compounds in AZIBs, emphasizing the methods to design electrode materials with desired structures, effective strategies to improve their electrochemical performance, and the fundamental electrochemical mechanisms. Finally, the current challenges and outlooks of oxygen-free vanadium-based compounds are proposed, providing a novel perspective and useful guidance for the design of high-performance vanadium-based cathode materials for AZIBs.

Key words: zinc-ion batteries, oxygen-free vanadium-based compound, energy storage mechanisms, electrochemical performance

贠潇如, 陈宇方, 肖培涛, 郑春满. 关于水系锌离子电池中无氧钒基正极材料的综述[J]. 电化学（中英文）, 2022, 28(11): 2219004.

Xiao-Ru Yun, Yu-Fang Chen, Pei-Tao Xiao, Chun-Man Zheng. Review on Oxygen-Free Vanadium-Based Cathodes for Aqueous Zinc-Ion Batteries[J]. Journal of Electrochemistry, 2022, 28(11): 2219004.

图/表 12

Material	Electrolyte	Voltage range/V	Specific capacity/mAh·g^-1(current density/ A·g^-1)	Capacity retention (current density/ A·g^-1; cycles numbers)	Ref.
VS₂	1 mol·L^-1 ZnSO₄	0.4 ~ 1.0	190.3 (0.05)	98% (0.5; 200)	[19]
VS₄@rGO	1 mol·L^-1 Zn(CF₃SO₃)₂	0.35 ~ 1.8	180 (1.0)	93.3% (1; 165)	[44]
VS₂@SS	1 mol·L^-1 ZnSO₄	0.4 ~ 1.0	198 (0.05)	80% (1; 1600)	[26]
VS₂@VOOH	3 mol·L^-1 ZnSO₄	0.4 ~ 1.0	184.2 (0.05)	82% (2.5; 400)	[70]
D-VS₂	1 mol·L^-1 ZnSO₄	0.2 ~ 1.7	262 (0.1)	94% (0.1; 100)	[43]
VS₂/VO_x	25 mol·L^-1 ZnCl₂	0.1 ~ 1.8	301 (0.05)	75% (1; 3000)	[20]
VS₄	1 mol·L^-1 ZnSO₄	0.2 ~ 1.6	310 (0.1)	-	[22]
VS₄/V₂O₃	3 mol·L^-1 Zn(CF₃SO₃)₂	0.3 ~ 1.2	163 (0.1)	/	[71]
VS₂/CC	PVA-Zn/Mn hydrogel	0.4 ~ 1.0	175 (0.2)	~65% (0.2; 40)	[72]
VS₂@N-C	3 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 1.8	203 (0.05)	97% (1; 600)	[36]
Mn-VS₄	1 mol·L^-1 Zn(OTf)₂ ACN/water (1:1)	0.3 ~ 2.0	547 (0.2)	97.83% (1; 1000)	[47]
V₂O₅·3H₂O@VS₂	3 mol·L^-1 ZnSO₄ EG/water (1:4)	0.3 ~ 1.6	290 (0.5)	69.7% (5; 6700)	[37]
VS₄/CNTs	2 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 1.7	265 (0.25)	93% (5; 1200)	[46]
1T-VS₂	2.5 mol·L^-1 Zn(CF₃SO₃)₂	0.4 ~ 0.85	212.9 (0.1)	86.7% (2; 2000)	[27]
VS₂	1 mol·L^-1 ZnSO₄	0.2 ~ 1.0	450.7 (0.1)	72% (1; 200)	[73]
VS₂·NH₃	2 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 1.7	392 (0.1)	110% (3; 2000)	[38]
VN_xO_y	2 mol·L^-1 ZnSO₄	0.4 ~ 1.4	240 (1)	95% (1; 50) 75% (20; 2000)	[58]
ZnO-QDs-VN-	1 mol·L^-1 Zn(CF₃SO₃)₂	0.4 ~ 1.6	384.1 (0.1)	~60% (5; 1800)	[23]
0.5O-VN	3 mol·L^-1 ZnSO₄	0.2 ~ 2.0	705 (0.2)	60.5% (1; 200)	[55]
VN@rGO	3 mol·L^-1 ZnSO₄	0.2 ~ 1.8	343 (0.2)	94.68% (1; 585) 91.24% (20; 10900)	[61]
VN	3.5 mol·L^-1 ZnSO₄	0.2 ~ 1.8	496 (0.1)	53.6% (20; 8000)	[74]
VN/C	3.5 mol·L^-1 ZnSO₄	0.2 ~ 1.8	321 (0.5)	76.6% (15; 6780) 95% (0.5; 720)	[75]
VN_xO_y/C	3 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 1.6	407.4 (0.5)	93.4% (5; 2000)	[21]
VN@NGr	3 mol·L^-1 ZnSO₄	0.2 ~ 1.8	~170 (0.5)	96.49% (0.1; 75) 70% (20; 26000)	[76]
VN/MXene	3 mol·L^-1 Zn(CF₃SO₃)₂	0.1 ~ 1.6	521 (0.5)	82.8% (5; 2000)	[59]
VN/NC	3 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 1.8	566 (0.2)	85% (10; 1000)	[57]
VN-rGO	1 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 2.0	809 (0.1)	78% (1; 400)	[60]
VSe₂	2 mol·L^-1 ZnSO₄	0.1 ~ 1.6	250.6 (0.2)	83% (2; 800)	[48]
VSe₂	2 mol·L^-1 ZnSO₄	0.2 ~ 1.6	131.8 (0.1)	80.8% (1; 500)	[49]
VSe_2-_x-SS	3 mol·L^-1 Zn(CF₃SO₃)₂	0.4 ~ 1.6	241.2 (0.2)	87.8% (4; 1800)	[50]
rGO-VSe₂	2 mol·L^-1 ZnSO₄	0.2 ~ 1.4	221.5 (0.5)	91.6% ( 0.5; 150)	[24]
Material	Electrolyte	Voltage range/V	Specific capacity/mAh·g^-1(current density/ A·g^-1)	Capacity retention (current density/ A·g^-1; cycles numbers)	Ref.
V₂O₅@V₂C	2.5 mol·L^-1 ZnSO₄	0.2 ~ 1.4	397 (0.5)	87% (4; 2000)	[77]
VO₂@V₂C	3 mol·L^-1 Zn(CF₃SO₃)₂	0.2 ~ 1.2	456 (0.2)	81% (5; 1000)	[67]
NVGO	6 mol·L^-1 KOH	1.2 ~ 2.1	253.9 (0.5)	70% (4.5; 500)	[78]
V₂CT_x	3 mol·L^-1 ZnSO₄+1 mol·L^-1 Li₂SO₄	0.25 ~ 1.6	423 (1.0)	~94% (30; 2000)	[79]
V₂O_x@V₂CT_x	1 mol·L^-1 ZnSO₄	0.2 ~ 1.6	304 (0.05)	81.6% (1; 200)	[66]
K-V₂C@MnO₂	2 mol·L^-1 ZnSO₄+0.25 mol·L^-1 MnSO₄	0.8 ~ 1.8	408.1 (0.3)	>100% (10; 10000)	[80]
MS-S-V₂CT_x	2 mol·L^-1 ZnSO₄	0.2 ~ 1.8	411.3 (0.5)	80% (10; 3000)	[25]
VSe₂@V₂CT_x	2 mol·L^-1 Zn(CF₃SO₃)₂	0.0 ~ 1.6	302.1 (0.1)	93.1% (2; 600)	[68]

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