钠离子电池炭基负极材料研究进展

doi:10.3866/PKU.WHXB201905003

物理化学学报 >> 2020, Vol. 36 >> Issue (5): 1905003.doi: 10.3866/PKU.WHXB201905003

所属专题：钠离子储能材料和器件

钠离子电池炭基负极材料研究进展

曹斌^1,²,李喜飞^1,^2,*()

¹ 西安理工大学，先进电化学能源研究院，材料科学与工程学院，西安 710048
² 陕西省储能材料表面技术国际联合研究中心，西安 710048

收稿日期:2019-05-02 录用日期:2019-07-31 发布日期:2019-08-09
通讯作者: 李喜飞 E-mail:xfli2011@hotmail.com
作者简介:李喜飞，2008年博士毕业于西安交通大学，现为西安理工大学教授。主要研究方向为新能源材料与器件
基金资助:
国家自然科学基金(51572194);国家自然科学基金(51672189);中国博士后科学基金(2018M643697);中国博士后科学基金(2019T120930)

Recent Progress on Carbon-based Anode Materials for Na-ion Batteries

Bin Cao^1,²,Xifei Li^1,^2,*()

¹ Institute of Advanced Electrochemical Energy, School of Materials Science and Engineering, Xi'an University of Technology, Xi'an 710048, P. R. China
² Shaanxi International Joint Research Centre of Surface Technology for Energy Storage Materials, Xi'an 710048, P. R. China

Received:2019-05-02 Accepted:2019-07-31 Published:2019-08-09
Contact: Xifei Li E-mail:xfli2011@hotmail.com
Supported by:
the National Natural Science Foundation of China(51572194);the National Natural Science Foundation of China(51672189);the China Postdoctoral Science Foundatio(2018M643697);the China Postdoctoral Science Foundatio(2019T120930)

摘要/Abstract

摘要：

钠离子电池是目前新兴的低成本储能技术，因在大规模电化学储能中具有较好的应用前景而受到了国内外学者广泛的关注与研究。作为钠离子电池的关键电极材料之一，非石墨的炭质材料因具有储钠活性高、成本低廉、无毒无害等诸多优点，而被认为是钠离子电池实际应用时负极的最佳选择。本文详细综述了目前钠离子电池炭基负极材料的研究进展，重点介绍了炭质材料的储钠机理与特性，分析了炭材料结构与电化学性能之间的关系，探讨了其存在的问题，为钠离子电池炭基负极材料的发展提供有益的认识。

关键词: 钠离子电池, 炭材料, 负极材料, 储钠机理, 研究进展

Abstract:

Na-ion batteries are currently an emerging and low-cost energy storage technology, which have attracted enormous attention and research due to its promising potentiality for large-scale energy storage applications. As the key electrode materials for Na-ion batteries, non-graphite carbonaceous materials have been regarded as the best choice for practical application due to its high sodium storage activity, low-cost and non-toxicity. According to the current research, graphite materials are not suitable to be anode materials of Na-ion batteries for practical application due to its low sodium storage capacity in carbonate electrolytes. Hard carbons have a high capacity of ~300 mAh·g^-1 with low sodium storage potential and thus are suitable for practical applications. Soft carbons have a sodium storage capacity about 200 mAh·g^-1 with sodium storage potential below 1 V vs. Na⁺/Na. Soft carbons usually exhibit excellent rate performances and thus are suitable to be used as anode materials for power Na-ion batteries. Reduced graphene oxide (rGO) has a sodium storage capacity of about 220 mAh·g^-1 and excellent rate performances. A high sodium storage capacity can be obtained by doping heteroatoms and introducing defect sites in rGO. However, the low material density, high sodium storage potential and large irreversible capacity of rGO will restrict its practical application. Porous carbons have high capacities of 300-450 mAh·g^-1 with excellent rate performances because their developed porous structure can provide more defects as the active sites for sodium storage and shorten the diffusion path of Na⁺ to improve rate performances. Carbon nanowires/fibers have good flexibility due to their unique one-dimensional feature and stable sodium storage reversible capacity with good rate performance. These materials have advantages to be flexible electrodes for sodium-based flexible energy storage devices. By introducing N, S and other heteroatoms, heteroatom-doped carbons have more active sites for sodium storage and thus achieve higher sodium storage capacity. In summary, carbon materials with low graphitization degree are important development directions for anode materials of low cost Na-ion batteries. New carbon materials with unique microstructure and morphology have higher sodium storage capacity and rate capability, so they can be used as high power anode materials for sodium storage. Considering many factors, such as cycle life, energy density, power density and manufacturing cost, of practical application, hard carbon anodes is currently the best choice for practical application of Na-ion batteries. In the future, improving SEI stability, increasing Coulombic efficiency and improving electrical conductivity of hard carbon are urgent problems to be solved for practical application. Herein, the recent progress of carbonaceous anode materials is reviewed. The sodium storage mechanism and characteristics of carbon materials are summarized and discussed. Furthermore, the relationship between micro-structures and electrochemical performances, and remained problems of carbon anodes are discussed. This review will promote the development and understanding of carbon anode materials for sodium storage.

Key words: Na-ion battery, Carbon material, Anode material, Sodium storage mechanism, Research progress

曹斌,李喜飞. 钠离子电池炭基负极材料研究进展[J]. 物理化学学报, 2020, 36(5), 1905003. doi: 10.3866/PKU.WHXB201905003

Bin Cao,Xifei Li. Recent Progress on Carbon-based Anode Materials for Na-ion Batteries[J]. Acta Physico-Chimica Sinica 2020, 36(5), 1905003. doi: 10.3866/PKU.WHXB201905003

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201905003

https://www.whxb.pku.edu.cn/CN/Y2020/V36/I5/1905003

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Materials	Electrolyte	Reversible capacity/(mAh g^-1)	Sodium storage potential	Initial Coulombic efficiency	Cyclability	Rate performances	Ref.
Graphite	1 mol·L^-1 NaPF₆ EC/DEMC	~0	-	-	-	-	28
Graphite	Ether-based Electrolyte	90-150	medium	~54%	2500 cycles at 0.5 A·g^-1	100 mAh·g^-1 at 5 A·g^-1	28, 35
Soft carbon	1 mol·L^-1 NaClO₄ EC/DEC	243	medium	71%	200 cycles at 0.05 A·g^-1	30 mAh·g^-1 at 0.5 A·g^-1	41
Soft carbon	1 mol·L^-1 NaPF₆ EC/DEC	90-250	medium	~60%	240 cycles at 1 A·g^-1	50-140 mAh·g^-1 at 1 A·g^-1	42
Hard carbon	0.8 mol·L^-1 NaPF₆ EC/DMC	190-222	low	81%	600 cycles at 0.06 A·g^-1	100-135 mAh·g^-1 at 0.3 A·g^-1	66
Hard carbon	1 mol·L^-1 NaPF₆ EC/DMC	300.6	low	89%	200 cycles at 0.03 A·g^-1	~50 mAh·g^-1 at 1.2 A·g^-1	67
Hard carbon	1 mol·L^-1 NaClO₄ EC/DEC	430.5	low	63%-70%	300 cycles at 0.2 A·g^-1	~100 mAh·g^-1 at 2 A·g^-1	68
rGO	1 mol·L^-1 NaClO₄ PC	217.2	high	~23%	1000 cycles at 0.04 A·g^-1	95.6 mAh·g^-1 at 1 A·g^-1	78
Porous carbon/Graphene	1 mol·L^-1 NaPF₆ PC/EC	670	high	~25%	1000 cycles at 1 A·g^-1	250 mAh·g^-1 at 1 A·g^-1	79
Porous carbon	1 mol·L^-1 NaClO₄ EC/DEC	331	high	45%	3000 cycles at 0.5 A·g^-1	53 mAh·g^-1 at 10 A·g^-1	41
Porous carbon	1 mol·L^-1 NaClO₄ PC + 5% FEC	255.5	high	35%	10000 cycles at 5 A·g^-1	90 mAh·g^-1 at 20 A·g^-1	87
Carbon nanofiber	1 mol·L^-1 NaOTf Diglyme	303	low	93%	10000 cycles at 10 A·g^-1	128 mAh·g^-1 at 20 A·g^-1	95
Nitrogen-rich porous carbon	1 mol·L^-1 NaClO₄ EC/DEC + 5% FEC	434.6	high	36.8%-41.6%	300 cycles at 0.05 A·g^-1	~100 mAh·g^-1 at 2 A·g^-1	85
Nitrogen-doped carbon/graphene	1 mol·L^-1 NaClO₄ EC/DEC	336	high	~50%	200 cycles at 0.05 A·g^-1	94 mAh·g^-1 at 5 A·g^-1	106
Sulfur-doped disorderedcarbon	1 mol·L^-1 NaClO₄ EC/DEC + 5% FEC	516	high	63.2%	1000 cycles at 1 A·g^-1	158 mAh·g^-1 at 4 A·g^-1	116

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钠离子电池炭基负极材料研究进展

Recent Progress on Carbon-based Anode Materials for Na-ion Batteries

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