Recent progress and application challenges in V-based polyanionic compounds for cathodes of sodium-ion batteries

doi:10.19799/j.cnki.2095-4239.2020.0179

Abstract

Abstract:

Sodium-ion batteries have potential applications in the field of electric bicycles, low-speed electric vehicles, and stationary energy storage due to the abundance and low cost of sodium resources. Of the various cathode materials proposed for sodium-ion batteries, vanadium (V)-based polyanionic compounds have become a research hotpot due to their high energy density, high power density, and stable structure. However, the low intrinsic conductivity and improper preparation method of such compounds impede their bulk electron and ion transfer, which limit the specific capacity, rate capability, and structure stability of these materials. In this review, starting from an analysis of the cell structure and sodium storage characteristics of several typical V-based polyanionic compounds, we review the charge transfer process, strategy for improving the kinetics, and progress in V-based polyanionic compounds from the perspective of the microstructure and mesoscopic electrode structure. Meanwhile, combined with a discussion of the practical applications of V-based polyanionic compounds, the important research directions to promote the further development of V-based polyanionic compounds are summarized.

Key words: sodium-ion batteries, cathode materials, V-based polyanionic compounds, charge transfer kinetics, low-cost and scale preparation, industrialization

CLC Number:

TQ 028.8

Hongming YI, Zhiqiang LYU, Huamin ZHANG, Mingming SONG, Qiong ZHENG, Xianfeng LI. Recent progress and application challenges in V-based polyanionic compounds for cathodes of sodium-ion batteries[J]. Energy Storage Science and Technology, 2020, 9(5): 1350-1369.

Figures/Tables 15

Fig.1

Table 1

Main characteristic parameters and performance data of some typical V-based polyanionic compounds"

材料体系	材料名称	晶体结构类型	氧化还原电对	氧化还原电位/V	理论比容量/mA·h·g^-1	理论能量密度 /W·h·kg^-1	储钠机理	钠扩散系数 /cm·s^-1	电化学性能
正磷酸盐	Na₃V₂(PO₄)₃^[11]	rhombohedral (NASICON, $R 3 ˉ c$ )	V⁴⁺/V³⁺	3.4	117.6	400	bi-phase reaction	1.06×10^-11 /CV	107.1 mA·h/g at 0.1 C
	Na₃V₂(PO₄)₃^[12]	rhombohedral (NASICON, $R 3 ˉ c$ )	V⁴⁺/V³⁺	3.4	117.6	400	bi-phase reaction	9.6×10^-11 /CV	117 mA·h/g at 1 C 82 mA·h/g at 100 C
	NaVOPO₄^[13]	monoclinic	V⁵⁺/V⁴⁺	3.6	145	522	single-phase reaction	1-3×10^–11 /GITT	101 mA·h/g at 5 C
	NaVOPO₄^[14]	orthorhombic	V⁵⁺/V⁴⁺	3.3	145	479	—	—	115 mA·h/g at 0.1 C
	KVOPO₄^[15]	orthorhombic	V⁵⁺/V³⁺	2.56	266.7	683		9.6 × 10^-12 /CV	235 mA·h/g at 0.05 C
	NaVOPO₄^[16]	tetragonal (layered structure)	—	—	—	—	—	—	—
	NaVOPO₄^[17]	triclinic	V⁵⁺/V⁴⁺	3.5	145	508	multi-phase reactions	4.9 × 10^-11 /EIS	144 mA·h/g at 0.05 C 58 mA·h/g at 5 C
	VOPO₄^[18]	tetragonal (layered structure)	V⁵⁺/V⁴⁺	3.4	165.5	563	—	—	150 mA·h/g at 0.05 C
	Na₃V₃(PO₄)₄^[19]	monoclinic (layered structure, C2/c)	V⁴⁺/V³⁺	3.9	44.5	174	—	—	>40 mA·h/g at 0.6 C 36.9 mA·h/g at 3 C
	Na₃V(PO₄)₂^[20]	monoclinic (layered structure, C2/c)	V⁴⁺/V³⁺	3.5	90	315	—	—	>90 mA·h/g at 0.2 C 71 mA·h/g at 15 C
	Na₄VO(PO₄)₂^[21]	orthorhombic (Pbca)	V⁵⁺/V⁴⁺	3.5	78	273	single-phase reaction	—	41.3 mA·h/g at 10 C
氟磷酸盐	NaVPO₄F^[22]	tetragonal (NASICON, I4/mmm)	V⁴⁺/V³⁺	3.7	142.5	485	—	—	120.9 mA·h/g at 0.05 C 70.1 mA·h/g at 0.5 C
	NaVPO₄F^[23]	monoclinic (NASICON, C2/c)	V⁴⁺/V³⁺	3.4	142.5	484.5	single-phase reaction	—	135 mA·h/g at 0.2 C 112 mA·h/g at 30 C
	Na₃V₂(PO₄)₂F₃^[24,25]	tetragonal (NASICON, P4₂/mnm)	V⁴⁺/V³⁺	3.9	128.3	500	bi-phase reaction and single-phase reaction	10^-12 /EIS	125 mA·h/g at 0.2 C 104 mA·h/g at 40 C 41 mA·h/g at 200 C
	Na₃V₂(PO₄)₂O₂F^[10,26]	tetragonal (I4/mmm)	V⁵⁺/V⁴⁺	3.8	130	494	two completely reversible bi-phasic reaction	—	127.4 mA·h/g at 0.2 C 84.1 mA·h/g at 40 C
	Na₃V₂(PO₄)₂O_1.6F_1.4^[27]	tetragonal (P4₂/mnm)	V⁵⁺/V^3.8+	3.8	155.6	592	single-phase reaction	2.4×10^-12 /EIS	134 mA·h/g at 0.1 C
焦磷酸盐	Na₇V₃(P₂O₇)₄^[28]	monoclinic (C2/c)	V⁴⁺/V³⁺	4.13	79.6	329	single-phase reaction	—	67.2 mA·h/g at 8 C
	Na₂(VO)P₂O₇^[29]	tetragonal (P21/c)	V⁵⁺/V⁴⁺	3.8	93.4	355	—	—	80 mA·h/g at 0.05 C
	NaVP₂O₇^[30]	monoclinic	V⁴⁺/V³⁺	3.9	108.1	421	—	—	104 mA·h/g at 0.1 C
混合聚阴离子型	Na₇V₄(P₂O₇)₄(PO₄)^[31]	tetragonal (P $4 ˉ$ 21c)	V⁴⁺/V³⁺	3.85	92.7	357	bi-phasic reaction	—	92 mA·h/g at 0.05 C 70.2 mA·h/g at 10 C

Table 1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

Fig.11

Fig.12

Fig.13

Fig.14

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