水系锌离子电池用钒基正极材料的研究进展

doi:10.3866/PKU.WHXB202005013

Abstract

Abstract:

In the past few decades, lithium-ion batteries (LIBs) have dominated the market of rechargeable batteries and are extensively applied in the field of electronic devices (e.g., mobile phones and computers). However, lack of lithium resources, high cost of lithium as well as toxic and flammable organic electrolytes significantly hinder further development and large-scale application of LIBs. Therefore, it is necessary to develop next-generation green rechargeable batteries to replace LIBs. Recently, aqueous zinc-ion batteries (AZIBs) have been considered as energy storage devices with substantial development prospects for future large-scale storage systems owing to their high safety performance, low production cost, abundant zinc resources, and environmental friendliness. Typically, we use zinc metal as the anode with neutral or weakly acidic aqueous electrolyte (pH: 3.6–6.0). However, cathode materials have high requirements for AZIBs while considering the charge effect of multivalent metal ions. Currently, one of the research emphases is to develop suitable zinc ion intercalation cathode materials with stable structures and high capacities. Among all types of cathode materials, vanadium-based compounds have the advantages of low cost and high reversible capacity. Additionally, their structure is variable, mainly including layered, tunneled and natrium super ionic conductor (NASICON) structure. Therefore, vanadium-based compounds have clear application possibility in AZIBs. However, there are still several significant problems. In particular, vanadium-based compounds generally have poor conductivity and low voltage platform. Electrochemical performance can be significantly improved mainly by pre-inserting metal ions or water molecules, optimizing the electrolyte, and controlling morphology of nanomaterials (nanosheets, nanospheres, etc.). In addition, the zinc storage mechanism in vanadium-based compounds is more complicated and controversial, including Zn²⁺ intercalation/deintercalation mechanism, co-insertion mechanism, and conversion reaction mechanism. Moreover, different materials usually exhibit different electrochemical properties and energy storage mechanisms. In this review, we comprehensively describe the energy storage mechanisms of vanadium-based compounds and discuss the application as well as development status of vanadium-based materials in AZIBs. Further, several strategies for improving their performance are proposed, including structural design (e.g., pre-insertion of metal ions or water molecules), morphology control (e.g., carbon coating), and electrolyte optimization (e.g., adjustment of composition and concentration). In particular, pre-insertion of metal ions or water molecules in the original structure can effectively solve these problems of low ion diffusion rate, poor conductivity, and structural instability, thereby achieving excellent electrochemical performance. Moreover, the application of a high-concentration electrolyte is a simple and effective strategy that can not only significantly widen the electrochemical stability window of the aqueous electrolyte but also suppress the dissolution of vanadium, thereby effectively improving energy density and cycling stability for AZIBs. Accordingly, the future development direction of AZIBs and their vanadium-based cathode materials is further prospected, aiming at designing high-performance electrode materials for AZIBs.

Key words: Aqueous zinc-ion battery, Cathode material, Vanadium-based compound, Electrolyte, Energy storage mechanism

Yongli Heng, Zhenyi Gu, Jinzhi Guo, Xinglong Wu. Research Progresses on Vanadium-Based Cathode Materials for Aqueous Zinc-Ion Batteries[J]. Acta Phys. -Chim. Sin. 2021, 37(3), 2005013. doi: 10.3866/PKU.WHXB202005013

Figures/Tables 11

Fig 1

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Table 1

Several vanadium-based cathode materials for AZIBs reported in recent years."

Materials morphology	Structure (space group)	Electrolyte	Ion (de-) intercalation mechanism	Discharge plateaus/V	Specific capacity/(mAh·g^-1)	Cycle number	Ref.
Bulk V₂O₅	Pmmn	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺, H₂O	0.42 and 0.85	470 (0.2 A·g^-1)	4000 (91.1%, 5 A·g^-1)	27
Porous V₂O₅	Pmmn	21 mol·L^-1 LiTFSI-1 mol·L^-1 Zn(CF₃SO₃)₂	Li⁺, Zn²⁺	0.90 and 1.10	238 (50 mA·g^-1)	2000 (80%, 2000 mA·g^-1)	33
V₂O₅ hollow nanospheres	Pmmn	3 mol·L^-1 Zn(SO₄)₂	Zn²⁺	0.56 and 0.85	327 (0.1 A·g^-1)	6000 (69.7%, 10 A·g^-1)	39
V₂O₅ nanosheets	Pmmn	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	0.47 and 0.88	503.1 (100 mA·g^-1)	700 (86%, 500 mA·g^-1)	40
V₂O₅@AB nanosheets	Pmmn	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	0.50 and 0.90	452 (0.1 A·g^-1)	5000 (92%, 10 A·g^-1)	41
V₂O₅·nH₂O nanowires/graphene (n = 1.29)	P1	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	0.54 and 0.91	372 (0.3 A·g^-1)	900 (71%, 6 A·g^-1)	46
V₂O₅·1.6H₂O nanosheets	P1	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	0.50 and 0.90	426 (0.1 A·g^-1)	5000 (95%, 10 A·g^-1)	42
Zn_0.25V₂O₅·nH₂O nanobelts	P${\rm{\bar 1}}$	1 mol·L^-1 Zn(SO₄)₂	Zn²⁺, H₂O	≈ 0.6, 0.8 and 1.0	282 (300 mA·g^-1)	1000 (80%, 3000 mA·g^-1)	25
Li_xV₂O₅·nH₂O nanosheets	P1	2 mol·L^-1 Zn(SO₄)₂	Zn²⁺	0.59, 0.82 and 0.96	407.6 (1 A·g^-1)	500 (76%, 5 A·g^-1)	47
Ca_0.25V₂O₅·nH₂O nanobelts	P1	1 mol·L^-1 Zn(SO₄)₂	Zn²⁺	≈ 0.7, 1.1 and 1.3	340 (0.05 A·g^-1)	3000 (96%, 20 A·g^-1)	49
Porous Mg_0.34V₂O₅·nH₂O nanobelts	P1	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺, Mg²⁺	≈ 0.4, 0.7 and 1.3	353 (50 mA·g^-1)	2000 (97%, 5000 mA·g^-1)	51
Cu_0.1V₂O₅·nH₂O nanosheets	P1	2 mol·L^-1 Zn(SO₄)₂	Zn²⁺	0.59, 0.81 and 0.96	359 (1 A·g^-1)	10000 (98%, 10 A·g^-1)	52
Ag_0.33V₂O₅ nanorods	C2/m	2 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	0.604, 0.915 and 1.082	200 (0.2 A·g^-1)	700 (3 A·g^-1)	50
VO₂(B) nanorods	C2/m	1 mol·L^-1 Zn(SO₄)₂	Zn²⁺	0.42, 0.51 and 0.74	325.6 (0.05 A·g^-1)	5000 (86%, 3 A·g^-1)	59
VO₂(B) nanorods/rGO	C2/m	1 mol·L^-1 Zn(SO₄)₂	Zn²⁺	0.55 and 0.78	365 (50 mA·g^-1)	200 (80%, 50 mA·g^-1)	60
VO₂(B)·0.2H₂O nanocuboids/graphene	C2/m	2 mol·L^-1 Zn(SO₄)₂	Zn²⁺	0.44 and 0.58	423 (0.25 A·g^-1)	1000 (87%, 8 A·g^-1)	61
VO₂(A) hollow spheres	P4₂/nmc	3 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	0.44, 0.52 and 0.90	357 (0.1 A·g^-1)	500 (76%, 5 A·g^-1)	56
VO₂(D) hollow nanospheres	P2₁/c	3 mol·L^-1 Zn(SO₄)₂	Zn²⁺, H₂O, H⁺	0.57 and 0.92	408 (0.1 A·g^-1)	10000 (58.2%, 10 A·g^-1)	62
Porous VO₂(M)/CNTs	P2₁/c	2 mol·L^-1 Zn(SO₄)₂	H⁺	0.55 and 0.85	248 (2 A·g^-1)	5000 (84.5%, 20 A·g^-1)	63
Na₃V₂(PO₄)₃/C nanoparticles	R3${\bar c}$	0.5 mol·L^-1 Zn(CH₃COO)₂	Zn²⁺	1.1	97 (50 mA·g^-1)	100 (74%, 50 mA·g^-1)	64
Na₃V₂(PO₄)₃@rGO microspheres	R3${\bar c}$	2 mol·L^-1 Zn(CF₃SO₃)₂	Na⁺, Zn²⁺	1.02 and 1.26	114 (50 mA·g^-1)	200 (75%, 500 mA·g^-1)	65
Na₃V₂(PO₄)₂F₃@C microparticles	P42/mnm	2 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	1.25 and 1.62	60 (0.2 A·g^-1)	4000 (95%, 1 A·g^-1)	66
VOPO₄ microsheets	Pbam	21 mol·L^-1 LiTFSI-1 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺	1.20, 1.34, 1.53 and 1.82	139 (0.05 A·g^-1)	1000 (93%, 5 A·g^-1)	67
VS₂ nanosheets	P${\rm{\bar 3}}$ml	1 mol·L^-1 Zn(SO₄)₂	Zn²⁺, H₂O	0.63 and 0.72	190.3 (0.05 A·g^-1)	200 (98%, 0.5 A·g^-1)	68
VS₄@rGO nanoparticles	I2/a	1 mol·L^-1 Zn(CF₃SO₃)₂	Zn²⁺ (and conversion mechanism)	0.54 and 0.89	180 (1 A·g^-1)	165 (83.3%, 1 A·g^-1)	69

Table 1

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Fig 8

Fig 9

Fig 10

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Research Progresses on Vanadium-Based Cathode Materials for Aqueous Zinc-Ion Batteries

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