水系钠离子电池的研究进展及实用化挑战

doi:10.6023/A20100492

化学学报 ›› 2021, Vol. 79 ›› Issue (4): 388-405.DOI: 10.6023/A20100492 上一篇下一篇

综述

水系钠离子电池的研究进展及实用化挑战

马慧¹, 张桓荣¹, 薛面起¹^,^*()

1 中国科学院理化技术研究所北京 100190

投稿日期:2020-10-26 发布日期:2021-02-22
通讯作者: 薛面起

作者简介:

马慧, 中国科学院理化技术研究所博士研究生. 2019在山东大学获得硕士学位, 2019年至今于中国科学院理化技术研究所攻读高分子化学与物理博士学位, 主要研究方向为水系二次离子电池.

张桓荣, 中国科学院理化技术研究所硕士研究生. 2019年在河北大学获得学士学位, 2019年至今于中国科学院理化技术研究所攻读高分子化学与物理硕士学位, 主要研究方向为水系二次电池电解液.

薛面起, 中国科学院理化技术研究所研究员. 2012年于中国人民大学获得博士学位. 2012~2014年就职于北京大学新材料学院, 任特聘研究员. 2014~2018年在中国科学院物理研究所工作. 现任中国科学院理化技术研究所研究员, 博士生导师, 主要研究领域为共轭高分子结晶和储能材料与器件.

基金资助:
中国科学院A类战略性先导科技专项(XDA21010214); 国家自然科学基金(21875266); 国家自然科学基金(21622407); 北京分子科学国家研究中心资助(BNLMS201909)

Research Progress and Practical Challenges of Aqueous Sodium-Ion Batteries

Hui Ma¹, Huanrong Zhang¹, Mianqi Xue¹^,^*()

1 Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2020-10-26 Published:2021-02-22
Contact: Mianqi Xue
About author:
* E-mail: xuemq@mail.ipc.ac.cn
Supported by:
Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21010214); National Natural Science Foundation of China(21875266); National Natural Science Foundation of China(21622407); Beijing National Laboratory for Molecular Sciences(BNLMS201909)

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摘要/Abstract

水系钠离子电池因其安全性高、成本低、环境友好等突出优势近些年来受到了广泛而深入的研究, 在取得巨大进展的同时也逐步开始了产业化进程. 但是与有机体系二次电池相比, 水系钠离子电池仍然极大地受限于电解液较窄的电化学稳定窗口和电极材料较差的循环稳定性. 迄今为止, 如何解决上述问题依然是这一领域发展的关键. 本综述主要概述了水系钠离子电池电极材料、电解液以及集流体的最新进展, 分析了开发高性能水系钠离子电池的挑战和可能的解决策略, 并进一步讨论了水系钠离子电池的发展前景.

关键词: 水系钠离子电池, 电极材料, 电解液, 能量密度, 循环寿命

Aqueous sodium-ion batteries recently have been widely and deeply studied in the energy field due to their prominent advantages such as high safety, low cost and environmental friendliness. Remarkable progresses of aqueous sodium-ion batteries gradually encourage their process of industrialization. However, compared with the organic secondary ion batteries, the development of aqueous sodium-ion batteries is limited by the narrow stable voltage window of the electrolyte and the poor cycle stability of the electrode material. How to solve these problems is still the key to the development of aqueous sodium-ion batteries. The latest developments in electrode materials, electrolyte and current collector of aqueous sodium-ion batteries, as well as challenges and possible solutions for developing high-performance aqueous sodium-ion batteries are mainly summarized in this review. Furthermore, the development prospects of aqueous sodium-ion batteries are discussed.

Key words: aqueous sodium-ion battery, electrode material, electrolyte, energy density, cycling life

引用此文

马慧, 张桓荣, 薛面起. 水系钠离子电池的研究进展及实用化挑战[J]. 化学学报, 2021, 79(4): 388-405.

Hui Ma, Huanrong Zhang, Mianqi Xue. Research Progress and Practical Challenges of Aqueous Sodium-Ion Batteries[J]. Acta Chimica Sinica, 2021, 79(4): 388-405.

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图/表 15

Figure 1. Electrode materials of aqueous sodium-ion batteries and their working voltage ranges[6]. Reprinted with permission from ref. [6]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

图2. (a~e) MnO2的晶体结构示意图[24]: (a) α-MnO 2, (b) β-MnO 2, (c) γ-MnO 2, (d) δ-MnO 2, (e) λ-MnO 2. (f) 不同晶型的MnO2在0.1 mol•L–1 NaSO4水系电解液中的循环伏安图(20 mV•s–1)[24]. 已获得参考文献[24]的转载许可, 版权所有© 2008 American Chemical Society

Figure 2. (a~e) Schematic of crystal structures[24]: (a) α-MnO 2, (b) β-MnO 2, (c) γ-MnO 2, (d) δ-MnO 2, (e) λ-MnO 2. (f) Cyclic voltammetry pattern of MnO2 with different crystalline structures in 0.1 mol•L–1 NaSO4 aqueous electrolyte (20 mV•s–1)[24]. Reprinted with permission from ref. [24]. Copyright © 2008 American Chemical Society

图3. Na0.66[Mn0.66Ti0.34]O2的Mn-L2,3 (a)和Ti-L2,3 (b)电子能量损失谱[43]. (c) Na0.66[Mn0.66Ti0.34]O2相对于Na+/Na的充放电曲线[43]. (d) Na0.66[Mn0.66Ti0.34]O2//NTP/C全电池2C倍率下的充放电曲线和[43]. Na0.66[Mn0.66Ti0.34]O2//NTP/C全电池的倍率性能(e)和循环稳定性(f)[43]. 已获得参考文献[43]的转载许可, 版权所有© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 3. Mn-L2,3 (a) and Ti-L2,3 (b) electron energy loss spectrum of Na0.66[Mn0.66Ti0.34]O2[43]. (c) Charge and discharge curves of Na0.66[Mn0.66Ti0.34]O2 vs. Na+/Na[43]. (d) Charge and discharge curves of Na0.66[Mn0.66Ti0.34]O2//NTP/C full battery at 2C rate[43]. Rate capability (e) and cycling stability (f) of Na0.66[Mn0.66Ti0.34]O2//NTP/C full battery[43]. Reprinted with permission from ref. [43]. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 4. The morphology (a) and rate capability (b) of Na0.58MnO2 electrode[53]. Charge and discharge curves at 1C rate (c) and cycle stability at 10C rate (d) of Na0.58MnO2//NTP full battery[53]. Reprinted with permission from ref. [53]. Copyright © 2016 The Royal Society of Chemistry

图5. Na2CoFe(CN)6晶体结构(a)和立方体形貌(b)[61]. Na2CoFe(CN)6电极在2C (1C=120 mA•g–1)倍率下的充放电曲线(c)和循环稳定性(d)[61]. Na2Zn3[Fe(CN)6]2//NTP全电池的充放电曲线(e)和循环稳定性(f)[62]. 已获得参考文献[61-62]的转载许可, 版权所有© 2019 The Royal Society of Chemistry和2019 American Chemical Society

Figure 5. Crystal structure (a) and cube morphology (b) of Na2CoFe(CN)6[61]. Charge-discharge curves (c) and cycling stability (d) of Na2CoFe(CN)6 electrode at 2C rate (1C=120 mA•g–1)[61]. Charge-discharge curves (e) and cycling stability (f) of Na2Zn3[Fe(CN)6]2//NTP full battery[62]. Reprinted with permission from ref. [61-62]. Copyright © 2019 The Royal Society of Chemistry and 2019 American Chemical Society

Figure 6. Cyclic voltammetry pattern at 0.1 mV•s–1 (a) and charge and discharge curves at 1C (b) of NVTP/C electrode[89]. Cycling stability (c) and charge and discharge curves (d) of NVTP/C and NVP/C electrodes[89]. Reprinted with permission from ref. [89]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

图7. Na2Ti1.5Mn0.5(PO4)3电极的倍率性能(a)和循环稳定性(b)[112]. NTP/石墨烯和纯的NTP电极在1 mol•L–1 NaSO4水系电解液中的循环伏安图(0.5 mV•s–1)(c)和循环稳定性(d)[113]. 已获得参考文献[112-113]的转载许可, 版权所有© 2019 The Royal Society of Chemistry和2014 The Royal Society of Chemistry

Figure 7. Rate performance (a) and cycling stability (b) of the Na2Ti1.5Mn0.5(PO4)3 electrode[112]. Cyclic voltammetry pattern (in 1 mol•L–1 NaSO4 aqueous electrolyte, 0.5 mV•s–1) (c) and cycling stability (d) of the NTP/graphene and NTP electrodes[113]. Reprinted with permission from ref. [112-113]. Copyright © 2019 The Royal Society of Chemistry and 2014 The Royal Society of Chemistry

图8. (a) PNP@CNTs复合材料电化学氧化还原机理[35]. (b) PNP@CNTs电极在1 mol•L–1 Na2SO4水系电解液中的循环伏安图(2 mV•s–1)[35]. (c) PNP@CNTs电极在10C倍率下的循环稳定性[35]. CuHCF//FeHCF水系钠离子全电池的工作原理示意图(d)、倍率性能(e)和循环稳定性(f)[74]. 已获得参考文献[35,74]的转载许可, 版权所有© 2016 The Royal Society of Chemistry和2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 8. (a) Electrochemical redox mechanism of PNP@CNTs[35]. (b) Cyclic voltammetry pattern of PNP@CNTs electrode in 1 mol•L–1 NaSO4 aqueous electrolyte (2 mV•s–1)[35]. (c) Cycling stability of PNP@CNTs electrode at 10C current density[35]. Schematic diagram of working principle (d), rate performance (e) and cycling stability (f) of CuHCF//FeHCF full battery[74]. Reprinted with permission from ref. [35,74]. Copyright © 2016 The Royal Society of Chemistry and 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

图9. (a) Na2Mn[Fe(CN)6]正极和KMn[Cr(CN)6]负极的恒流充放电曲线[65]. (b) Na2Mn[Fe(CN)6]//KMn[Cr(CN)6]全电池的循环稳定性[65]. (c) Na0.66[Mn0.66Ti0.34]O2//NTP全电池在0.2C倍率条件下的恒流充放电曲线[45]. (d) Na0.66[Mn0.66Ti0.34]O2//NTP全电池在不同水系电解液中的循环稳定性(NaSiWE: 2 mol•kg–1 NaCF3SO3; NaWiSE: 9.26 mol•kg–1 NaCF3SO3)[45]. 已获得参考文献[65,45]的转载许可, 版权所有© 2018 WILEY-VCH Verlag GmbH & Co. KGaA和2017 WILEY-VCH Verlag GmbH & Co. KGaA

Figure 9. (a) Charge and discharge curves of Na2Mn[Fe(CN)6] cathode and KMn[Cr(CN)6] anode[65]. (b) Cycling stability of the Na2Mn[Fe(CN)6]//KMn[Cr(CN)6] full battery[65]. (c) Charge-discharge curves of the Na0.66[Mn0.66Ti0.34]O2//NTP full battery at 0.2C rate[45]. (d) Cycling stability of the Na0.66[Mn0.66Ti0.34]O2//NTP full battery in different aqueous electrolytes (NaSiWE: 2 mol•kg–1 NaCF3SO3; NaWiSE: 9.26 mol•kg–1 NaCF3SO3)[45]. Reprinted with permission from ref. [65,45]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim and 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

图10. 不同凝胶含量的NVP@C//ALO/CMK-3全电池的线性扫描伏安图(5 mV•s–1)(a)和循环稳定性(b)[120]. KZHCF//NTP@C全电池的示意图(c)和倍率性能(d)[59]. 已获得参考文献[120,59]的转载许可, 版权所有© 2018 American Chemical Society和2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 10. The linear sweep voltammogram curves (5 mV•s–1) (a) and cycling performances (b) of NVP@C//ALO/CMK-3 full batteries with different gel contents[120]. Schematic illustration of (c) and rate performances (d) of the KZHCF//NTP@C full battery[59]. Reprinted with permission from ref. [120,59]. Copyright © 2018 American Chemical Society and 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Type (Based cathode)	Cathode	Anode	Current collector	Electrolyte	AV. Voltage/V	Capacity/ (mAh•g^-1)	Retention/% (No. of cycles)	Ref.
Mn-based oxides	γ-MnO₂	Zn	—	7 M NaOH+ 1 M ZnSO₄	1.3	225 (250 A•cm^-2)	76 (25)	^[27]
	λ-MnO₂	AC	graphite sheet and stainless steel foil	1 M Na₂SO₄	1.2	—(3C)	100 (5000)	^[28]
	Na_0.44MnO₂	NVP/C	—	1 M Na₂SO₄	0.7	117 (1C)	94.8 (200)	^[30]
	Na_0.44MnO₂	NTP@C	stainless steel mesh	1 M Na₂SO₄	1.0	42 (0.1 A•g^-1)	62 (1000)	^[31]
	Na_0.44MnO₂	NTP	—	1 M Na₂SO₄	1.0	50 (7C)	50 (1600)	^[32]
	Na_0.44MnO₂	Na₂V₆O₁₆•nH₂O	nickel foam	1 M Na₂SO₄	0.9	62 (0.04 A•g^-1)	40 (30)	^[33]
	Na_0.44MnO₂	NTP/C	nickel foam	1 M Na₂SO₄	0.8	50 (50C)	100 (75)	^[34]
	Na_0.44MnO₂	PNP@CNT	titanium mesh	1 M Na₂SO₄	0.8	92 (5C)	89 (200)	^[35]
	Na_0.44MnO₂/CNT	Zn	carbon foil	1 M Na₂SO₄+0.5 M ZnSO₄	—	—	—	^[36]
	Na_0.44MnO₂	PPy-CNT	titanium mesh	1 M Na₂SO₄	0.7	99.2 (0.1 A•g^-1)	94 (100)	^[37]
	Na_0.44MnO₂	TiP₂O₇	—	1 M Na₂SO₄	~0.8	40 (2.5 mA•g^-1)	—	^[38]
	Na_0.44MnO₂	FePO₄	titanium mesh	1 M Na₂SO₄	0.7	70 (3C)	87 (300)	^[39]
	Na_0.44MnO₂	AC	—	1 M Na₂SO₄	0.8	45 (4C)	~100 (1000)	^[41]
	Na_0.66[Mn_0.66Ti_0.34]O₂	NTP	titanium mesh	1 M Na₂SO₄	1.2	76 (2C)	88 (300)	^[43]
	Na_0.66[Mn_0.66Ti_0.34]O₂	NTP/C	titanium mesh	5 M NaClO₄	1.0	100 (2C)	33 (300)	^[44]
	Na_0.66[Mn_0.66Ti_0.34]O₂	Na_1.5Ti_1.5Fe_0.5(PO₄)₃/C	titanium mesh	5 M NaClO₄	1.0	109.5 (2C)	97.4 (300)	^[44]
	Na_0.66[Mn_0.66Ti_0.34]O₂	NTP	stainless steel grid	9.26 m NaCF₃SO₃	1.0	31 (0.2C)	70 (350)	^[45]
	Na_0.27MnO₂	Na_0.27MnO₂	carbon paper	1 M Na₂SO₄	1.1	88 (1 A•g^-1)	100 (5000)	^[50]
	Na_0.35MnO₂	PPy@MoO₃	nickel mesh	0.5 M Na₂SO₄	0.8	25 (0.55 A•g^-1)	79 (1000)	^[51]
	K_0.34MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	0.8	64 (0.2 A•g^-1)	84.1 (200)	^[52]
	K_0.15Na_0.26MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	1.0	65 (0.2 A•g^-1)	92 (200)	^[52]
	Na_0.58MnO₂·0.48H₂O	NTP	titanium mesh	1 M Na₂SO₄	1.4	39 (10C)	94 (1000)	^[53]
	NaMnO₂	NTP	titanium mesh	2 M NaAc	1.15	37 (5C)	75 (500)	^[55]
	K_0.27MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	0.7	80 (0.2 A•g^-1)	83 (100)	^[56]
	K_0.27MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	0.8	80 (0.2 A•g^-1)	86 (100)	^[57]
	K_0.27MnO₂	AC	—	1 M Na₂SO₄	0.9	60 (0.2 A•g^-1)	75 (200)	^[58]
Prussian blue analogues	Na₂CuFe(CN)₆	NTP	titanium mesh	1 M Na₂SO₄	1.4	86 (10C)	88 (1000)	^[20]
	Na₂CoFe(CN)₆	NTP	titanium mesh	1 M Na₂SO₄	0.8	100 (5C)	100 (100)	^[60]
	Na₂Zn₃[Fe(CN)₆]₂	NTP	titanium mesh	17 m NaClO₄	1.6	47 (10C)	100 (1000)	^[62]
	Na₂Mn[Fe(CN)₆]	TiS₂	titanium sheet (cathode) and aluminum foil (anode)	15 M NaClO₄	1.75	38 (5C)	92 (1000)	^[64]
	Na₂Mn[Fe(CN)₆]	KMn[Cr(CN)₆]	titanium mesh	17 m NaClO₄	>2	27 (30C)	78 (100)	^[65]
	Na₂Mn[Fe(CN)₆]	NTP/C	aluminum foil	32 M Kac+ 8 M NaAc	0.82	50 (0.1 A•g^-1)	36 (100)	^[66]
	Na₂Mn[Fe(CN)₆]	Zn	titanium mesh	1 M Na₂SO₄+1 M ZnSO₄+SDS	1.0	≈130 (5C)	75 (2000)	^[67]
Type (Based cathode)	Cathode	Anode	Current collector	Electrolyte	AV. Voltage/V	Capacity/ (mAh•g^-1)	Retention/% (No. of cycles)	Ref.
	Na₂Mn[Fe(CN)₆]	Na₃Fe₂(PO₄)₃	—	17 m NaClO₄	0.9	59 (5C)	75 (700)	^[68]
	Na_1.88Mn[Fe(CN)₆]_0.971.35 H₂O	NaTiOPO₄	—	9 m NaOTF+ 22 m TEAOTF	1.74	40 (0.25C)	90 (200)	^[69]
	NaFeHCN	AC	carbon paper	2 M NaNO₃+ 60 wt% maltose	0.8	74.4 (2 A•g^-1)	87 (2000)	^[70]
	Na₂NiFe(CN)₆	NTP	titanium mesh	1 M Na₂SO₄	1.27	79 (5C)	88 (250)	^[72]
	Na_1.45Ni[Fe(CN)₆]_0.87· 3.02 H₂O	NTP@C	stainless steel mesh	5 M NaClO₄	1.4	61.4 (0.1 A•g^-1)	83 (600)	^[73]
	Na_1.90Cu_0.95[Fe(CN)₆] 1.9 H₂O	Na_1.32Fe- [Fe(CN)₆]_0.87 2.0 H₂O	graphite sheet	saturated NaNO₃ solution	0.7	50 (5C)	86 (250)	^[74]
	K₂Zn₃(Fe(CN)₆)₂ 9 H₂O	NTP	carbon cloth	NaClO₄-PVA gel	1.6	0.56 mAh• cm^-2 (10 A•cm^-2)	90.2 (300)	^[59]
	Zn₃[Fe(CN)₆]₂	NTP/C	titanium mesh	NaClO₄-H₂O-PEG	1.6	69 (2C)	>91 (100)	^[78]
	CuHCFe	MnHCMn	carbon cloth	10 M NaClO₄+Mn(ClO₄)₂ solution	0.95	23 (10C)	100 (1000)	^[81]
	K_0.8V_1.8O_xFe(CN)₆	WO₃	titanium mesh	NaClO₄-H₂O-PEG	—	67 (1 A•g^-1)	90.3 (2000)	^[82]
	InFe(CN)₆	NTP-CNT	—	Na₂SO₄-CMC gel	1.55	38 mAh•cm^-2 (0.3 A•cm^-2)	91 (300)	^[83]
Polyanionic compounds	NVP	NTP	nickel foam	1 M Na₂SO₄	1.2	58 (10 A•g^-1)	50 (50)	^[86]
	NaFePO₄/AlF₃	AC	stainless-steel mesh	1 M Na₂SO₄	—	95.6 (1 C)	58.4 (50)	^[91]
	NaFePO₄	AC	stainless-steel mesh	1 M Na₂SO₄	—	101.7 (1 C)	39.6 (50)	^[91]
	Na₂FeP₂O₇	NTP	nickel mesh	2 M Na₂SO₄	—	45 (2 mA•cm^-2)	82 (30)	^[94]
	Na₂FeP₂O₇	NTP	nickel mesh	4 M NaClO₄	—	45 (2 mA•cm^-2)	93 (30)	^[94]
	Na₄Fe₃(PO₄)₂(P₂O₇)	NTP	stainless steel mesh	17 m NaClO₄	2	44 (1C)	75 (200)	^[95]
	Na₃V₂(PO₄)₂F₃-CNT	NTP-CNT	carbon paper (cathode) and titanium foil (anode)	17 m NaClO₄	1.7	75 (0.5C)	74 (20)	^[97]
	Na₃(VOPO₄)₂F	NTP	titanium mesh (cathode) and stainless steel mesh (anode)	35 m NaFSI	1.4	72 (1C)	83 (500)	^[98]
	Na₃V₂O₂_x(PO₄)₂F_3-2_x- CNT	NTP/C	carbon paper	10 M NaClO₄+ 2 vol% VC	1.45	39 (10C)	85 (200)	^[100]
	Na₂FePO₄F	NTP	titanium mesh	17 m NaClO₄	0.7	85 (1 mA•cm^-2)	64 (100)	^[101]
	Na₃MnPO₄CO₃	NTP	titanium mesh	5 M NaNO₃	0.8	68 (0.2 C)	96 (50)	^[109]
	NaVPO₄F	polyimide	stainless steel mesh	5 M NaNO₃	0.9	40 (0.05 A•g^-1)	75 (20)	^[117]
	NVP	PPTO	Pb (cathode) titanium mesh (anode)	5 M NaNO₃	1.0	201 (1C)	79 (80)	^[119]
	NVP/C	alloxazine/CMK-3	stainless steel mesh	NaCF₃SO₃-PAM gel	1.03	160 (2C)	90 (100)	^[120]
Other	NaNi_0.4Co_0.6O₂	AC	stainless steel mesh	0.5 M Na₂SO₄	0.7	105 (0.8 A•g^-1)	95 (500)	^[103]
Other	PPy	alizarin	carbon cloth	NaClO₄-PVA gel	1.0	152 (1.0 A•g^-1)	—	^[106]

Type (Based cathode)	Cathode	Anode	Current collector	Electrolyte	AV. Voltage/V	Capacity/ (mAh•g^-1)	Retention/% (No. of cycles)	Ref.
Mn-based oxides	γ-MnO₂	Zn	—	7 M NaOH+ 1 M ZnSO₄	1.3	225 (250 A•cm^-2)	76 (25)	^[27]
	λ-MnO₂	AC	graphite sheet and stainless steel foil	1 M Na₂SO₄	1.2	—(3C)	100 (5000)	^[28]
	Na_0.44MnO₂	NVP/C	—	1 M Na₂SO₄	0.7	117 (1C)	94.8 (200)	^[30]
	Na_0.44MnO₂	NTP@C	stainless steel mesh	1 M Na₂SO₄	1.0	42 (0.1 A•g^-1)	62 (1000)	^[31]
	Na_0.44MnO₂	NTP	—	1 M Na₂SO₄	1.0	50 (7C)	50 (1600)	^[32]
	Na_0.44MnO₂	Na₂V₆O₁₆•nH₂O	nickel foam	1 M Na₂SO₄	0.9	62 (0.04 A•g^-1)	40 (30)	^[33]
	Na_0.44MnO₂	NTP/C	nickel foam	1 M Na₂SO₄	0.8	50 (50C)	100 (75)	^[34]
	Na_0.44MnO₂	PNP@CNT	titanium mesh	1 M Na₂SO₄	0.8	92 (5C)	89 (200)	^[35]
	Na_0.44MnO₂/CNT	Zn	carbon foil	1 M Na₂SO₄+0.5 M ZnSO₄	—	—	—	^[36]
	Na_0.44MnO₂	PPy-CNT	titanium mesh	1 M Na₂SO₄	0.7	99.2 (0.1 A•g^-1)	94 (100)	^[37]
	Na_0.44MnO₂	TiP₂O₇	—	1 M Na₂SO₄	~0.8	40 (2.5 mA•g^-1)	—	^[38]
	Na_0.44MnO₂	FePO₄	titanium mesh	1 M Na₂SO₄	0.7	70 (3C)	87 (300)	^[39]
	Na_0.44MnO₂	AC	—	1 M Na₂SO₄	0.8	45 (4C)	~100 (1000)	^[41]
	Na_0.66[Mn_0.66Ti_0.34]O₂	NTP	titanium mesh	1 M Na₂SO₄	1.2	76 (2C)	88 (300)	^[43]
	Na_0.66[Mn_0.66Ti_0.34]O₂	NTP/C	titanium mesh	5 M NaClO₄	1.0	100 (2C)	33 (300)	^[44]
	Na_0.66[Mn_0.66Ti_0.34]O₂	Na_1.5Ti_1.5Fe_0.5(PO₄)₃/C	titanium mesh	5 M NaClO₄	1.0	109.5 (2C)	97.4 (300)	^[44]
	Na_0.66[Mn_0.66Ti_0.34]O₂	NTP	stainless steel grid	9.26 m NaCF₃SO₃	1.0	31 (0.2C)	70 (350)	^[45]
	Na_0.27MnO₂	Na_0.27MnO₂	carbon paper	1 M Na₂SO₄	1.1	88 (1 A•g^-1)	100 (5000)	^[50]
	Na_0.35MnO₂	PPy@MoO₃	nickel mesh	0.5 M Na₂SO₄	0.8	25 (0.55 A•g^-1)	79 (1000)	^[51]
	K_0.34MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	0.8	64 (0.2 A•g^-1)	84.1 (200)	^[52]
	K_0.15Na_0.26MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	1.0	65 (0.2 A•g^-1)	92 (200)	^[52]
	Na_0.58MnO₂·0.48H₂O	NTP	titanium mesh	1 M Na₂SO₄	1.4	39 (10C)	94 (1000)	^[53]
	NaMnO₂	NTP	titanium mesh	2 M NaAc	1.15	37 (5C)	75 (500)	^[55]
	K_0.27MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	0.7	80 (0.2 A•g^-1)	83 (100)	^[56]
	K_0.27MnO₂	NTP	stainless steel mesh	1 M Na₂SO₄	0.8	80 (0.2 A•g^-1)	86 (100)	^[57]
	K_0.27MnO₂	AC	—	1 M Na₂SO₄	0.9	60 (0.2 A•g^-1)	75 (200)	^[58]
Prussian blue analogues	Na₂CuFe(CN)₆	NTP	titanium mesh	1 M Na₂SO₄	1.4	86 (10C)	88 (1000)	^[20]
	Na₂CoFe(CN)₆	NTP	titanium mesh	1 M Na₂SO₄	0.8	100 (5C)	100 (100)	^[60]
	Na₂Zn₃[Fe(CN)₆]₂	NTP	titanium mesh	17 m NaClO₄	1.6	47 (10C)	100 (1000)	^[62]
	Na₂Mn[Fe(CN)₆]	TiS₂	titanium sheet (cathode) and aluminum foil (anode)	15 M NaClO₄	1.75	38 (5C)	92 (1000)	^[64]
	Na₂Mn[Fe(CN)₆]	KMn[Cr(CN)₆]	titanium mesh	17 m NaClO₄	>2	27 (30C)	78 (100)	^[65]
	Na₂Mn[Fe(CN)₆]	NTP/C	aluminum foil	32 M Kac+ 8 M NaAc	0.82	50 (0.1 A•g^-1)	36 (100)	^[66]
	Na₂Mn[Fe(CN)₆]	Zn	titanium mesh	1 M Na₂SO₄+1 M ZnSO₄+SDS	1.0	≈130 (5C)	75 (2000)	^[67]
Type (Based cathode)	Cathode	Anode	Current collector	Electrolyte	AV. Voltage/V	Capacity/ (mAh•g^-1)	Retention/% (No. of cycles)	Ref.
	Na₂Mn[Fe(CN)₆]	Na₃Fe₂(PO₄)₃	—	17 m NaClO₄	0.9	59 (5C)	75 (700)	^[68]
	Na_1.88Mn[Fe(CN)₆]_0.971.35 H₂O	NaTiOPO₄	—	9 m NaOTF+ 22 m TEAOTF	1.74	40 (0.25C)	90 (200)	^[69]
	NaFeHCN	AC	carbon paper	2 M NaNO₃+ 60 wt% maltose	0.8	74.4 (2 A•g^-1)	87 (2000)	^[70]
	Na₂NiFe(CN)₆	NTP	titanium mesh	1 M Na₂SO₄	1.27	79 (5C)	88 (250)	^[72]
	Na_1.45Ni[Fe(CN)₆]_0.87· 3.02 H₂O	NTP@C	stainless steel mesh	5 M NaClO₄	1.4	61.4 (0.1 A•g^-1)	83 (600)	^[73]
	Na_1.90Cu_0.95[Fe(CN)₆] 1.9 H₂O	Na_1.32Fe- [Fe(CN)₆]_0.87 2.0 H₂O	graphite sheet	saturated NaNO₃ solution	0.7	50 (5C)	86 (250)	^[74]
	K₂Zn₃(Fe(CN)₆)₂ 9 H₂O	NTP	carbon cloth	NaClO₄-PVA gel	1.6	0.56 mAh• cm^-2 (10 A•cm^-2)	90.2 (300)	^[59]
	Zn₃[Fe(CN)₆]₂	NTP/C	titanium mesh	NaClO₄-H₂O-PEG	1.6	69 (2C)	>91 (100)	^[78]
	CuHCFe	MnHCMn	carbon cloth	10 M NaClO₄+Mn(ClO₄)₂ solution	0.95	23 (10C)	100 (1000)	^[81]
	K_0.8V_1.8O_xFe(CN)₆	WO₃	titanium mesh	NaClO₄-H₂O-PEG	—	67 (1 A•g^-1)	90.3 (2000)	^[82]
	InFe(CN)₆	NTP-CNT	—	Na₂SO₄-CMC gel	1.55	38 mAh•cm^-2 (0.3 A•cm^-2)	91 (300)	^[83]
Polyanionic compounds	NVP	NTP	nickel foam	1 M Na₂SO₄	1.2	58 (10 A•g^-1)	50 (50)	^[86]
	NaFePO₄/AlF₃	AC	stainless-steel mesh	1 M Na₂SO₄	—	95.6 (1 C)	58.4 (50)	^[91]
	NaFePO₄	AC	stainless-steel mesh	1 M Na₂SO₄	—	101.7 (1 C)	39.6 (50)	^[91]
	Na₂FeP₂O₇	NTP	nickel mesh	2 M Na₂SO₄	—	45 (2 mA•cm^-2)	82 (30)	^[94]
	Na₂FeP₂O₇	NTP	nickel mesh	4 M NaClO₄	—	45 (2 mA•cm^-2)	93 (30)	^[94]
	Na₄Fe₃(PO₄)₂(P₂O₇)	NTP	stainless steel mesh	17 m NaClO₄	2	44 (1C)	75 (200)	^[95]
	Na₃V₂(PO₄)₂F₃-CNT	NTP-CNT	carbon paper (cathode) and titanium foil (anode)	17 m NaClO₄	1.7	75 (0.5C)	74 (20)	^[97]
	Na₃(VOPO₄)₂F	NTP	titanium mesh (cathode) and stainless steel mesh (anode)	35 m NaFSI	1.4	72 (1C)	83 (500)	^[98]
	Na₃V₂O₂_x(PO₄)₂F_3-2_x- CNT	NTP/C	carbon paper	10 M NaClO₄+ 2 vol% VC	1.45	39 (10C)	85 (200)	^[100]
	Na₂FePO₄F	NTP	titanium mesh	17 m NaClO₄	0.7	85 (1 mA•cm^-2)	64 (100)	^[101]
	Na₃MnPO₄CO₃	NTP	titanium mesh	5 M NaNO₃	0.8	68 (0.2 C)	96 (50)	^[109]
	NaVPO₄F	polyimide	stainless steel mesh	5 M NaNO₃	0.9	40 (0.05 A•g^-1)	75 (20)	^[117]
	NVP	PPTO	Pb (cathode) titanium mesh (anode)	5 M NaNO₃	1.0	201 (1C)	79 (80)	^[119]
	NVP/C	alloxazine/CMK-3	stainless steel mesh	NaCF₃SO₃-PAM gel	1.03	160 (2C)	90 (100)	^[120]
Other	NaNi_0.4Co_0.6O₂	AC	stainless steel mesh	0.5 M Na₂SO₄	0.7	105 (0.8 A•g^-1)	95 (500)	^[103]
Other	PPy	alizarin	carbon cloth	NaClO₄-PVA gel	1.0	152 (1.0 A•g^-1)	—	^[106]

表1. 水系钠离子全电池的电化学性能

Table 1. Electrochemical properties of aqueous sodium-ion full batteries

表1. 水系钠离子全电池的电化学性能

Table 1. Electrochemical properties of aqueous sodium-ion full batteries

图11. 以Na3MnTi(PO4)3为电极的对称水系钠离子全电池示意图(a)和循环稳定性(b)[144]. 碳分层包覆的NTP复合材料的结构示意图(c)和循环稳定性(d)[34]. 已获得参考文献[144,34]的转载许可, 版权所有© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim和2015 The Royal Society of Chemistry

Figure 11. Schematic illustration (a) and cycling performances (b) of aqueous symmetric sodium-ion full battery based Na3MnTi(PO4)3 electrode[144]. Schematic illustration (c) and cycling performances (d) of hierarchical carbon coated NTP composites[34]. Reprinted with permission from ref. [144,34]. Copyright © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim and 2015 The Royal Society of Chemistry

Figure 12. (a) Al和Ti箔在32 mol•L–1 KAc+8 mol•L–1 NaAc电解液中的线性伏安图[66]; (b) NTP/C和Na2MnFe(CN)6电极在32 mol•L–1 KAc+8 mol•L–1 NaAc电解液中循环伏安图[66]; (c) 9 mol•kg–1 NaOTF和9 mol•kg–1 NaOTF+22 mol•kg–1 TEAOTF电解液的电化学稳定窗口[69]. 已获得参考文献[66,69]的转载许可, 版权所有© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim和2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim (a) Linear sweep voltammetry of Al and Ti foil in 32 mol• L–1 KAc+8 mol•L–1 NaAc electrolyte[66]. (b) Cyclic voltammetry of NTP/C和Na2MnFe(CN)6 electrode in 32 mol•L–1 KAc+8 mol•L–1 NaAc electrolyte[66]. (c) The electrochemical voltage window of 9 mol• kg–1 NaOTF and 9 mol•kg–1 NaOTF+22 mol•kg–1 TEAOTF electrolyte[69]. Reprinted with permission from ref. [66,69]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim and 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

图13. 高浓糖基钠离子电解液与不同离子电解液的电化学稳定窗口(a)和离子电导率(b)[70]. (c) 高浓糖基钠离子电解液的温度适用性[70]. (d) 基于不同电解液的NaFeHCN//AC全电池的循环稳定性[70]. (e) 高浓糖基钠离子电解液的拉曼光谱[70]. 已获得参考文献[70]的转载许可, 版权所有© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 13. Electrochemical stability windows (a) and conductivity (b) of the sugar-based ultra-concentrated sodium-ion electrolytes and other electrolytes[70]. (c) Temperature applicability of the sugar-based ultra-concentrated sodium-ion electrolytes[70]. (d) Cycling stability of the NaFeHCN//AC full battery based on different electrolytes[70]. (e) Raman spectra of the sugar-based ultra-concentrated sodium-ion electrolytes[70]. Reprinted with permission from ref. [70]. Copyright © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

图14. (a) CNT-CNF集流体的示意图[157]; (b) ACC和CNT-CNF膜在5.0 mol•L–1 H2SO4水系电解液中的循环伏安图(0.5 mV•s–1)[157]; (c) ACC和CNT-CNF集流体电化学测试前后的光学图片[157]; (d) CNT-CNF膜在5.0 mol•L–1 H2SO4水系电解液中不同时间的循环伏安图(0.5 mV•s–1)[157]. 已获得参考文献[157]的转载许可, 版权所有© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 14. (a) Schematic illustrations of CNT-CNF current collector[157]. (b) Cyclic voltammetry pattern of the ACC and CNT-CNF films in 5.0 mol•L–1 H2SO4 aqueous electrolyte (0.5 mV•s–1)[157]. (c) Optical images of ACC and CNT-CNF current collectors before and after electrochemical testing[157]. (d) Cyclic voltammetry pattern of the CNT-CNF film in 5.0 mol•L–1 H2SO4 aqueous electrolyte with different time (0.5 mV•s–1)[157]. Reprinted with permission from ref. [157]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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