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化学进展 2022, Vol. 34 Issue (9): 2051-2062 DOI: 10.7536/PC220121 前一篇   后一篇

• 综述 •

钠离子混合电容器电极材料的研究进展

戚琦1,*(), 徐佩珠1, 田志东2, 孙伟2, 刘杨杰2, 胡翔2,*()   

  1. 1 赣南师范大学化学化工学院 赣州 341000
    2 中国科学院福建物质结构研究所 福州 350002
  • 收稿日期:2022-01-18 修回日期:2022-02-17 出版日期:2022-09-20 发布日期:2022-04-01
  • 作者简介:

    戚琦 副教授,2000年于北京师范大学化学学院获硕士学位。目前就职于赣南师范大学化学化工学院。研究方向为光谱分析,纳米材料的设计合成及其应用, 电传感新方法的研究等,参与完成国家自然基金课题4项,专利1项,发表论文近20余篇。

    胡翔 博士,2021年于福州大学材料科学与工程学院获博士学位。目前为中国科学院福建物质结构研究所特别研究助理。研究方向为新型碳基复合材料的设计合成及其在电化学储能器件中的应用,包括锂、钠、钾离子电池及金属离子混合电容器等,研究成果在Energy Environ. Sci.、Nat. Commun.、Adv. Energy Mater.、Adv. Funct. Mater.、ACS Nano、Energy Storage Mater.、Nano-Micro Lett.、Small、J. Mater. Chem. A等能源及材料期刊发表论文30余篇,其中第一/通讯作者15篇。

  • 基金资助:
    国家自然科学基金项目(21875253); 中国科学院科研装备开发项目(YJKYYQ20190007); 中国科学院国际合作局国际伙伴计划(121835KYSB20200039); 中国博士后科学基金(2021TQ0331); 中国博士后科学基金(2021M700147)
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Recent Advances of the Electrode Materials for Sodium-Ion Capacitors

Qi Qi1(), Peizhu Xu1, Zhidong Tian2, Wei Sun2, Yangjie Liu2, Xiang Hu2()   

  1. 1 School of Chemistry and Chemical Engineering, Gannan Normal University,Ganzhou 341000, China
    2 Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,Fuzhou 350002, China
  • Received:2022-01-18 Revised:2022-02-17 Online:2022-09-20 Published:2022-04-01
  • Contact: *e-mail: qiqichem@163.com(Qi Qi);huxiang@fjirsm.ac.cn(Xiang Hu)
  • Supported by:
    National Natural Science Foundation of China(21875253); Scientific Research and Equipment Development Project of CAS(YJKYYQ20190007); CAS-Commonwealth Scientific and Industrial Research Organization (CSIRO) Joint Research Projects(121835KYSB20200039); China Postdoctoral Science Foundation(2021TQ0331); China Postdoctoral Science Foundation(2021M700147)

钠离子混合电容器(SIHCs)因其资源丰富和价格低廉等优点,同时具有与锂相似的物理化学性质,被认为是最具有发展前景的电化学储能器件之一。通常,SIHCs由高能量密度的阳极和高功率密度的阴极组成,可在钠离子电池和超级电容器之间搭建能量和功率的桥梁。然而,电容型正极材料和电池型负极材料之间的动力学和容量的不平衡问题成为实现其规模化应用的主要瓶颈。本文概述了SIHCs相关的工作原理和各类正、负极材料研究进展,从材料结构的可控制备和改性处理等方面对SIHCs发展趋势进行了重点评述,并讨论了SIHCs发展过程中遇到的主要挑战,最后对该领域在未来的研究方向进行了展望。

关键词： 钠离子混合电容器, 电容型正极, 电池型负极, 动力学, 容量

Sodium ion hybrid capacitors (SIHCs) have been considered to be one of the most promising electrochemical energy storage devices because of the abundant and low cost of sodium resources, and their similar physical and chemical properties to that of the lithium. SIHCs are usually assembled with high-energy anode and high-power cathode, which can bridge the energy and power gaps between sodium-ion batteries and supercapacitors. However, their large-scale application is strongly impeded by the kinetics and capacity imbalance between capacitive-type cathode and battery-type anode. In this paper, the working principle of SIHCs and the research progress of various anode and cathode materials are summarized. The development trend of SIHCs is reviewed emphatically from the aspects of controlled preparation and modification of material structure. The main challenges encountered in the development of SIHCs are discussed and the future research direction of the electrode materials in this field is prospected.

Contents

1 Introduction

2 Operating principle

3 Cathode materials

3.1 Activated carbon

3.2 Carbon nanotube

3.3 Graphene

3.4 MXene

4 Anode materials

4.1 Intercalation materials

4.2 Conversion materials

4.3 Alloying materials

5 Conclusion and outlook

Key words: sodium ion hybrid capacitors, capacitive-type cathode, battery-type anode, kinetics, capacity
()
图1 钠离子混合电容器的工作原理图
Fig. 1 Working principle illustration of typical SIHCs
图2 (a,b)ANCN的TEM和元素分布图[26];(c)N/S-HCNs的TEM图;(d,e)HCN,N-HCN,S-HCN,和N/S-HCN对离子的吸附能对比以及对PF6-吸附的电荷密度差异[27]
Fig.2 (a, b) TEM and elemental mapping images of the ANCN[26]; (c) TEM image of the N/S-HCNs, (d, e) the comparison of ion adsorption energy for HCN, N-HCN, S-HCN and N/S-HCN, and the charge density difference for PF6-[27]
表1 各类正极材料的电化学性能比较
Table 1 The electrochemical performance comparison of different cathode materials
Materials Potential range
(V)		 Specific capacity/current
density (A·g-1)		 Cycle number/current density
(A·g-1)		 Capacity retention rate ref
3DFAC 2.5~4.2 151 F·g-1 (1) 2000 (5) 93.4% 19
ZDPC 1.5~4.0 218.4 F·g-1 (0.1) 2000 (1) 87% 20
MnSAs/NF-CNs 2.5~4.2 87 mAh·g-1 (0.1) 2000 (2) 86.2% 22
CNTs 0~1.0 200 F·g-1 (20) — — 25
ANCN 2.6~4.2 166.5 F·g-1 (0.1) 2000 (1) ~100% 26
OCG 2.5~4.2 105 mAh·g-1 (0.1) 3000 (1) 91% 30
MG 2.0~4.2 414 F·g-1 (0.1) — — 31
MXene/AAC -0.8~1.2 378 F·g-1 (0.5) 10000 (5) 97.4% 36
图3 (a)V2CTx的合成示意图及嵌钠机理图,(b)HC/V2CTx构成的SIHCs机理图及(c)不同电流密度下充放电曲线图[37]
Fig. 3 (a) Schematic illustration of the synthesis of V2CTx and its sodium intercalation, (b) schematic illustration of the charge-storage mechanisms for HC/V2CTx SIHCs device and (c) galvanostatic charge-discharge profiles at different current densities[37]
图4 (a)钠离子在TiO2@PBC中扩散机理图,(b)TiO2@PBC//AC SIHCs装置在不同电流密度下的充放电曲线图[50]; (c)TiO2@CNT@C的SEM图,插图为其TEM图,(d)TiO2@CNT@C//BAC构成的SIHCs装置与其他储能装置的性能对比,(e)TiO2@CNT@C//BAC构成的SIHCs长循环性能[51]
Fig. 4 (a) Schematic diagram of Na+ diffusion in TiO2. (b) Galvanostatic charge-discharge profiles at different current densities of TiO2@PBC//AC SIHCs device[50];(c) SEM and TEM images of the TiO2@CNT@C, (d) performance comparison for the TiO2@CNT@C//BAC SIHCs device and currently available energy-storage systems, (e) long-term cycle performance of TiO2@CNT@C//BAC SIHCs device[51]
图5 (a, b) 3D-IO FeS-QDs@NC的SEM和TEM图[57]; (c, d) SnS2/GCA的SEM图[59]; (e, f) MoSe2/G的SEM和TEM图[13]
Fig. 5 (a, b) SEM and TEM images of the 3D-IO FeS-QDs@NC[57]; (c, d) SEM images of the SnS2/GCA[59]; (e, f) TEM images of the MoSe2/G[13]
图6 能量与功率密度对比Ragone曲线图
Fig. 6 Ragone plots of the SIHCs device compared with previously reported SIHCs
表2 不同负极/正极构成的钠离子混合电容器电化学性能比较
Table 2 The electrochemical performance comparison based on different anode/cathode SHICs devices
Anode/
Cathode		 Potential
Range
(V)		 Max energy
Density
(Wh·kg-1)		 Max power
density
(W·kg-1)		 Cycling life ref
NaBi//AC 1.5~3.5 106.3 11100 98.6% after 2000 cycles 2 A·g-1 10
MoSe2/G//AC 0.5~3 82 10752 81% after 5000 cycles 5 A·g-1 13
3DFC//3DFAC 0~4.0 111 20000 75.6% after 15000 cycles 2 A·g-1 19
MnSAs/NF-CNs//
MnSAs/NF-CNs		 0~4.0 197 9350 85.2% after 10000 cycles 1 A·g-1 22
PSNC-3-800//
PSOC-A		 1.5~3.5 201 16500 72% after 10000 cycles 6.4 A·g-1 43
SCN-A//SCN-A 0~4.0 112 12000 85% after 3000 cycles 5 A·g-1 44
N-HCNWs//AC 0.5~4.0 108 9000 70% after 2000 cycles 2 A·g-1 45
NHPC-800//NHPAC 0~4.0 115 — — 46
TiO2-x/CNT//AC/CNT 1.0~4.0 109 5000 73% after 2000 cycles 2 A·g-1 49
TiO2-800s@PBC//AC 1.0~4.0 91 13000 71% after 5000 cycles 2 A·g-1 50
TiO2@CNT@C//BAC 1.0~4.0 81.2 12400 85.3% after 5000 cycles 1 A·g-1 51
SnO2/graphene//CNTs 0~4.0 86 4100 100% after 900 cycles 0.5 A·g-1 52
A-SnO2@PCNS//HPC 0~4.0 196.4 28100 72% after 5000 cycles 5 A·g-1 53
3D-IO FeS-QDs@NC//AC 0.5~3.4 151.8 9280 91% after 5000 cycles 1 A·g-1 57
SnS2/ZnS-RGO-180//PCPSK-3 0.01~4.5 145.6 13500 100% after 1000 cycles 1 A·g-1 58
SnS2/GCA//A-KB 1.0~4.3 108.3 6053 68.4% after 1500 cycles 1 A·g-1 59
NCHS//WS2@NCNs 0.5~4.2 134.7 4700 90% after 2000 cycles 0.2 A·g-1 60
Bi NAMPS//B, N-co-doped C 0.2~3.1 93 33000 92% after 5000 cycles 20 A·g-1 65
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