钠离子电池钒基聚阴离子型正极材料的发展现状与应用挑战

易红明, 吕志强, 张华民, 宋明明, 郑　琼, 李先锋

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

Hongming YI, Zhiqiang LYU, Huamin ZHANG, Mingming SONG, Qiong ZHENG, Xianfeng LI

表1 典型的钒基聚阴离子型化合物的主要特征参数和性能水平

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, $R \overset{ˉ}{3} c$ )	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, $R \overset{ˉ}{3} c$ )	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 $\overset{ˉ}{4}$ 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