聚阴离子型钠离子电池正极材料的研究进展

doi:10.3866/PKU.WHXB201905017

Abstract

Abstract:

Because of their high energy density and long cycle life, lithium-ion batteries (LIBs) have dominated the portable electronics market for over 20 years. However, with the increasing demand for large-scale energy storage systems for grid applications, the price of Li resources has increased owing to the low abundance of Li in Earth's crust and non-uniform distribution on the planet. Because Na has similar physical and chemical properties as Li and is an abundant natural resource, room-temperature sodium-ion batteries (SIBs) are expected to be among the most promising next-generation large grid energy storage devices. It is known that the cathode, anode, separator and electrolyte materials are the main components of batteries. Among these, Na-containing cathode materials are of critical importance. As a cathode material for SIBs, polyanion-type compounds have become a hot research topic owing to their versatile structural frameworks, high thermal stabilities, high ambient stabilities even in the charging state, small volume changes, tunable operating voltage by tuning the chemical environment of the polyanions, and high operating voltages owing to the inductive effects of the polyanionic groups (PO₄³⁻, SO₄²⁻, SiO₄⁴⁻, etc.). In particular, for Earth's abundant resources and inherent stability, polyanion-based compounds are suitable for large-scale stationary energy storage. Taking grid balancing into account, batteries with fast charge rates are in demand, which requires cathodes having high rate capability. However, despite the presence of ion diffusion channels in polyanion compounds, the electronic transport channels are blocked owing to the separation of the metal polyhedral and the strong electronegativity of the anions, leading to poor electron conductivity, which largely limits the rate capability of polyanion compounds. Therefore, it is crucial to understand the inherent limitation of the kinetics in terms of the structural aspects and to determine strategies for improving the rate capability. This review discusses the intrinsic reasons for the factors impacting ion diffusion based on the different structures of polyanion-type cathodes. From the perspectives of surface modification and morphology, strategies for enhancing the transport of sodium ions and electrons at the surface and interface are summarized and discussed. Then, from the standpoint of the hierarchical structures of materials to the design of a structural framework, which have been rarely reported, this review proposes schemes that intrinsically enhance the rate capability of polyanion compounds and provides a perspective on developments that can further improve the rate capability of cathode materials. This review provides suggestions for designing and optimizing high-rate polyanion-type and other kinds of cathodes from both academic and practical viewpoints.

Key words: Sodium-ion battery, Polyanion-type cathode, High rate capability, Ion diffusion, Electron transport

Wenli Pan,Wenhao Guan,Yinzhu Jiang. Research Advances in Polyanion-Type Cathodes for Sodium-Ion Batteries[J]. Acta Physico-Chimica Sinica 2020, 36(5), 1905017. doi: 10.3866/PKU.WHXB201905017

Figures/Tables 10

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Table 1

Table 2

Rate performance of polyanion cathodes for sodium ion batteries."

Chemical formula	Theoretical Capacity/(mAh?g^?1)	Materials and ways to improve rate performance	Electrochemical data	Ref.
Maricite-NaFePO₄	150	Nano-NaFePO₄ (50 nm)/C	142 mAh?g^?1 at C/20 and 60 mAh?g^?1 at 2C	20
		Nano-NaFePO₄ (40–140 nm)/C/graphene	142 mAh?g^?1 at C/20 and 51 mAh?g^?1 at 5C	62
		Nano-NaFePO₄ (1.6 nm) @ porous N-doped carbon nanofibers	145 mAh?g^?1 at 0.2C and 61 mAh?g^?1 at 50C	53
Oviline-NaFePO₄	150	Bare NaFePO₄	125 mAh?g^?1 at 7.5 mA?g^?1	17
Oviline-NaFePO₄	150	Polythiophene-Wrapped NaFePO₄	141 mAh?g^?1 at 10 mA?g^?1 and 42 mAh?g^?1 at 300 mA?g^?1	64
Na₂FeP₂O₇	97	Na₂FeP₂O₇ (300-500 nm)/C	82 mAh?g^?1 at C/20 and 50 mAh?g^?1 at 10C	65
Na₂FeP₂O₇	97	Na₂FeP₂O₇/MWCNT	86 mAh?g^?1 at 1C and 68 mAh?g^?1 at 10C	57
Na₃V₂(PO₄)₃	118	Na₃V₂(PO₄)₃/C	93 mAh?g^?1 at C/20 and 29 mAh?g^?1 at 1C	66
		Na₃V₂(PO₄)₃ (20-40 nm) @ Porous Carbon Matrix	102 mAh?g^?1 at 20C and 44 mAh?g^?1 at 200C	28
		Na₃V₂(PO₄)₃ (50-200 nm) @C@rGO	115 mAh?g^?1 at 20C and 86 mAh?g^?1 at 100C	67
Na₃V₂(PO₄)₂F₃	128	Core/double-shell structured Na₃V₂(PO₄)₂F₃@C	120 mAh?g^?1 at 1C and 63 mAh?g^?1 at 100C	68
Na₃(VO)₂(PO₄)₂F	130	Na₃(VO)₂(PO₄)₂F /C	102 mAh?g^?1 at 20C and 68 mAh?g^?1 at 1C	69
Na₃(VO)₂(PO₄)₂F	130	Graphene quantum dots-shielded Na₃(VO)₂(PO₄)₂F @C nanocuboids	102 mAh?g^?1 at 20C and 70 mAh?g^?1 at 45C	60
Na₂Fe(SO₄)₂· 2H₂O	82	Bare- Na₂Fe(SO₄)₂·2H₂O	70 mAh?g^?1 at C/20	42
Na₂Fe(SO₄)₂· 2H₂O	82	Na₂Fe(SO₄)₂·2H₂O@ zero-, one and two-dimensional carbon matrix (activated carbon, single wall carbon nanotubes and graphene)	60 mAh?g^?1 at 5C	44
Na_2+2xFe_2-x(SO₄)₃ (x = 0–0.4)	120	Bare Na_2+2xFe_2?x(SO₄)₃	102 mAh?g^?1 at C/20 and 58 mAh?g^?1 at 20C	49
Na_2+2xFe_2-x(SO₄)₃ (x = 0–0.4)	120	Na_2+2xFe_2?x(SO₄)₃/SWNT	60 mAh?g^?1 at 40C	51
Na₂FeSiO₄	276	Na₂FeSiO₄ (30–50 nm)/C	106 mAh?g^?1 at 10 mA?g^?1 and 40 mAh?g^?1 at 200 mA?g^?1	34
		Na₂FeSiO₄ (20–50 nm)/C	106 mAh?g^?1 at 27.6 mA g^?1 (0.1C) and 100 mAh?g^?1 at 276 mA?g^?1 (1C)	35
		mesoporous Na₂FeSiO₄ nanospheres @ carbon nanotubes	173 mAh?g^?1 at 0.1C and 109 mAh?g^?1 at 20C	70
Na₂MnSiO₄	280	Na₂MnSiO₄ with 5% (volume percent) VC electrolyte additive	210 mAh?g^?1 at 0.1C and 100 mAh?g^?1 at 5C	37
Na₂MnSiO₄	280	three-dimensionally ordered macroporous Na₂MnSiO₄/C	207 mAh?g^?1 at 0.1C and 76 mAh?g^?1 at 5C	38

Table 2

Fig 7

Fig 8

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Research Advances in Polyanion-Type Cathodes for Sodium-Ion Batteries

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	Chemical formula	Space group	Dimensions of ion channels	Sodium diffusion coefficient/(cm²·s^?1)	Ref.
Phosphates	Maricite-NaFePO₄	Pnma	none	4.79 × 10^?11 (nano amorphous particles)	20
	Olivine-NaFePO₄	Pnma	one	8.63 × 10^?17	18
	Na₂FeP₂O₇	P${\rm{\bar 1}}$	three	(2.79–8.45) × 10^?13	57
	Na₂CoP₂O₇	P${\rm{\bar 1}}$	three	/	23
		P21cn	two	/	23
		P42/mnm	three	/	23
	Na₃V₂(PO₄)₃	R${\rm{\bar 3}}$cH	three	4.59 × 10^?13–2.45 × 10^?10	58
	Na₃V₂(PO₄)₂F₃	P42/mnm	three	2.68 × 10^?12	59
	Na₃(VO)₂(PO₄)₂F	P42/mnm	three	(1–3) × 10^?10	60
Sulfates	Na₂Fe(SO₄)₂·2H₂O	P21/c	two	10^?14	44
	Na₂Fe(SO₄)₂·4H₂O	P21/c	one	/	45
	NaFe(SO₄)₂	C12/m1	two	9.01 × 10^?10 (1273 K)	47
	Na_2+2xFe_2?x(SO₄)₃	P21/c	three	1 × 10^?7	61
Orthosilicate	Na₂FeSiO₄	P${\rm{\bar 1}}$	three	(1.92–2.53) × 10^?13	35
	Na₂MnSiO₄	Pn	one	2.37 × 10^?15–8.62 × 10^?14	38
	Na₂CoSiO₄	Pn2a	Three	1.29 × 10^?13–1.06 × 10^?12	40