石墨烯在锂离子电容器中的应用研究进展

doi:10.19799/j.cnki.2095-4239.2020.0041

摘要/Abstract

摘要：

锂离子电容器结合了锂离子电池和超级电容器的储能机理，综合了两者各自的优良性能，具有能量密度大、功率密度高、循环寿命长和安全性能好等优点，是目前电化学储能领域的研究热点。石墨烯是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢晶格的二维碳纳米材料，具高比表面积、高导电性、高容量以及物理化学性质稳定等优点，被认为是下一代高性能锂离子电容器的理想电极材料。本文综述了石墨烯在锂离子电容器中的应用，介绍了其作为锂离子电容器正极与负极材料的电化学性能及优缺点，进一步阐明了石墨烯的比表面积、电导率及微观形貌等因素对其电化学性能的影响。此外，还介绍了元素掺杂石墨烯与石墨烯复合材料等改性手段，分析了石墨烯中的杂原子对其电负性、片层结构、活性位点及电化学性能的影响，并且分类总结了近期较为常见的几种石墨烯复合电极材料，进一步说明了改性石墨烯在锂离子电容器中的应用与进展，并在最后对石墨烯基锂离子电容器的发展前景进行了展望。

关键词: 锂离子电容器, 石墨烯, 能量密度, 功率密度

Abstract:

Lithium-ion capacitors (LICs) are hybrid energy storage devices that can bridge the gap between lithium-ion batteries and supercapacitors. Therefore, they have become a popular research topic owing to their advantages of high energy density, high power density, long cycle life, and good safety. Graphene, which is a two-dimensional (2D) honeycomb lattice of sp2-bonded carbon atoms, is promising for future applications in electrochemical energy storage fields because of its high specific surface area, high conductivity, high capacity, and stable physicochemical properties. In this study, a critical overview of the current progress related to the usage of graphene materials in LICs is presented. The effects of specific surface area, electrical conductivity, and micromorphology on the electrochemical performance of graphene were also summarized. In addition, a brief summary of the structural modification of the graphene electrode materials is presented, followed by a systematic examination of the usage of doped graphene and graphene-based composites as electrode materials in LICs. The effects of heteroatoms on the electronegativity, microstructure, active sites, and electrochemical properties of graphene are also analyzed. Finally, major challenges associated with the future applications of graphene materials in LICs are presented.

Key words: lithium-ion capacitors, graphene, energy density, power density

中图分类号:

TM 911

刘腾宇, 张熊, 安亚斌, 李晨, 马衍伟. 石墨烯在锂离子电容器中的应用研究进展[J]. 储能科学与技术, 2020, 9(4): 1030-1043.

LIU Tengyu, ZHANG Xiong, AN Yabin, LI Chen, MA Yanwei. Research progress on the application of graphene for lithium-ion capacitors[J]. Energy Storage Science and Technology, 2020, 9(4): 1030-1043.

图/表 6

参考文献 48

1	DUBAL D P, AYYAD O, RUIZ V, et al. Hybrid energy storage: The merging of battery and supercapacitor chemistries[J]. Chemical Society Reviews, 2015, 44(7): 1777-1790.
2	WANG G P, ZHANG L, ZHANG J J. A review of electrode materials for electrochemical supercapacitors[J]. Chemical Society Reviews, 2012, 41(2): 797-828.
3	WANG H, ZHU C, CHAO D, et al. Nonaqueous hybrid lithium-ion and sodium-ion capacitors[J]. Advanced Materials, 2017, 29(46): 1702039
4	LAHEAAR A, JANES A, LUST E. Electrochemical properties of carbide-derived carbon electrodes in non-aqueous electrolytes based on different Li-salts[J]. Electrochimica Acta, 2011, 56(25): 9048-9055.
5	WANG H W, ZHANG Y, ANG H X, et al. A high-energy lithium-ion capacitor by integration of a 3D interconnected titanium carbide nanoparticle chain anode with a pyridine-derived porous nitrogen-doped carbon cathode[J]. Advanced Functional Materials, 2016, 26(18): 3082-3093.
6	LI B, ZHENG J, ZHANG H, et al. Electrode materials, electrolytes, and challenges in nonaqueous lithium-ion capacitors[J]. Advanced Materials, 2018, 30(17): 1705670.
7	ZHENG J P. High energy density electrochemical capacitors without consumption of electrolyte[J]. Journal of the Electrochemical Society, 2009, 156(7): A500-A505.
8	黄晓斌, 张熊, 韦统振, 等. 超级电容器的发展及应用现状[J]. 电工电能新技术, 2017, 36(11): 63-70.
	HUANG X B, ZHANG X, WEI T Z, et al. Development and application status of super capacitors[J]. Advanced Technology of Electrical Engineering and Energy, 2017, 36(11): 63-70.
9	LI C, ZHANG X, SUN C, et al. Recent progress of graphene-based materials in lithium-ion capacitors[J]. Journal of Physics D: Applied Physics, 2019, 52(14): 3001.
10	张熊, 马衍伟. 电化学超级电容器电极材料的研究进展[J]. 物理, 2011, 40(10): 656-663.
	ZHANG X, MA Y W. Recent advances in the development of electrode materials for supercapacitor[J]. Physical, 2011, 40(10): 656-663.
11	刘文杰, 孙现众, 郝青丽. 电化学沉积制备MnO₂-PEDOT-PSS复合材料及其电容特性研究[J]. 储能科学与技术, 2018, 7(2): 262-269.
	LIU W J, SUN X Z, HAO Q L. Electrochemical deposition of MnO₂/PEDOT-PSS composite and its capacitance characteristics[J]. Energy Storage Science and Technology, 2018, 7(2): 262-269.
12	NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696): 666-669.
13	VELICKY M, BRADLEY D F, COOPER A J, et al. Electron transfer kinetics on mono-and multilayer graphene[J]. ACS Nano, 2014, 8(10): 10089-10100.
14	SEOL J H, JO I, MOORE A L, et al. Two-dimensional phonon transport in supported graphene[J]. Science, 2010, 328(5975): 213-216.
15	ZHANG X, ZHANG H T, LI C, et al. Recent advances in porous graphene materials for supercapacitor applications[J]. RSC Advances, 2014, 4(86): 45862-45884.
16	EL-KADY M F, SHAO Y L, KANER R B. Graphene for batteries, supercapacitors and beyond[J]. Nature Reviews Materials, 2016, 1(7): 16033.
17	WANG Y G, SONG Y F, XIA Y Y. Electrochemical capacitors: Mechanism, materials, systems, characterization and applications[J]. Chemical Society Reviews, 2016, 45(21): 5925-5950.
18	SIVAKUMAR C, NIAN J N, TENG H S. Poly(o-toluidine) for carbon fabric electrode modification to enhance the electrochemical capacitance and conductivity[J]. Journal of Power Sources, 2005, 144(1): 295-301.
19	LIU J. Charging graphene for energy[J]. Nature Nanotechnology, 2014, 9(10): 739-741.
20	LEE J H, SHIN W H, RYOU M H, et al. Functionalized graphene for high performance lithium ion capacitors[J]. ChemSusChem, 2012, 5(12): 2328-2333.
21	MHAMANE D, ARAVINDAN V, KIM M S, et al. Silica-assisted bottom-up synthesis of graphene-like high surface area carbon for highly efficient ultracapacitor and li-ion hybrid capacitor applications[J]. Journal of Materials Chemistry A, 2016, 4(15): 5578-5591.
22	LI H, SHEN L, WANG J, FANG S, et al. Three-dimensionally ordered porous TiNb₂O₇ nanotubes: A superior anode material for next generation hybrid supercapacitors[J]. Journal of Materials Chemistry A, 2015, 3(32): 16785-16790.
23	GOKHALE R, ARAVINDAN V, YADAV P, et al. Oligomer-salt derived 3D, heavily nitrogen doped, porous carbon for Li-ion hybrid electrochemical capacitors application[J]. Carbon, 2014, 80: 462-471.
24	ZHANG T, ZHANG F, ZHANG L, et al. High energy density Li-ion capacitor assembled with all graphene-based electrodes[J]. Carbon, 2015, 92: 106-118.
25	ZHANG L, ZHANG F, YANG X, et al. Porous 3D graphene-based bulk materials with exceptional high surface area and excellent conductivity for supercapacitors[J]. Scientific Reports, 2013, 3: 1408.
26	YOSHIO M, WANG H Y, FUKUDA K, et al. Effect of carbon coating on electrochemical performance of treated natural graphite as lithium-ion battery anode material[J]. Journal of the Electrochemical Society, 2000, 147(4): 1245-1250.
27	YOO E, KIM J, HOSONO E, et al. Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries[J]. Nano Letters, 2008, 8(8): 2277-2282.
28	WU Z S, REN W C, XU L, et al. Doped graphene sheets as anode materials with superhigh rate and large capacity for lithium ion batteries[J]. ACS Nano, 2011, 5(7): 5463-5471.
29	孙现众, 张熊, 王凯, 等. 高能量密度的锂离子混合型电容器[J]. 电化学, 2017, 23(5): 586-603.
	SUN X Z, ZHANG X, WANG K, et al. High energy density lithium ion hybrid capacitor[J]. Electrochemistry, 2017, 23(5): 586-603.
30	REN J J, SU L W, QIN X, et al. Pre-lithiated graphene nanosheets as negative electrode materials for Li-ion capacitors with high power and energy density[J]. Journal of Power Sources, 2014, 264: 108-113.
31	SUN Y, TANG J, QIN F, et al. Hybrid lithium-ion capacitors with asymmetric graphene electrodes[J]. Journal of Materials Chemistry A, 2017, 5(26): 13601-13609.
32	LI C, ZHANG X, WANG K, et al. Scalable self-propagating high-temperature synthesis of graphene for supercapacitors with superior power density and cyclic stability[J]. Advance Materials, 2017, 29(7): 1604690.
33	LI C, ZHANG X, WANG K, et al. High-power and long-life lithium-ion capacitors constructed from N-doped hierarchical carbon nanolayer cathode and mesoporous graphene anode[J]. Carbon, 2018, 140: 237-248.
34	ASWATHY R, KESAVAN T, KUMARAN K T, et al. Octahedral high voltage LiNi_0.5Mn_1.5O₄ spinel cathode: enhanced capacity retention of hybrid aqueous capacitors with nitrogen doped graphene[J]. Journal of Materials Chemistry A, 2015, 3(23): 12386-12395.
35	LIU M, ZHANG L X, HAN P X, et al. Controllable formation of niobium nitride/nitrogen-doped graphene nanocomposites as anode materials for lithium-ion capacitors[J]. Particle & Particle Systems Characterization, 2015, 32(11): 10061011.
36	WU A S, TAN Y Z, ZHENG S H, et al. Bottom-up fabrication of sulfur-doped graphene films derived from sulfur-annulated nanographene for ultrahigh volumetric capacitance micro-supercapacitors[J]. Journal of the American Chemical Society, 2017, 139(12): 4506-4512.
37	ZHANG X L, LU Z S, FU Z M, et al. The mechanisms of oxygen reduction reaction on phosphorus doped graphene: A first-principles study[J]. Journal of Power Sources, 2015, 276: 222-229.
38	LUAN Y T, HU R, FANG Y Z, et al. Nitrogen and phosphorus dual-doped multilayer graphene as universal anode for full carbon-based lithium and potassium ion capacitors[J]. Nano-Micro Letters, 2019, 11(1): 30.
39	BOKHARI S W, SIDDIQUE A H, PAN H, et al. Nitrogen doping in the carbon matrix for Li-ion hybrid supercapacitors: State of the art, challenges and future prospective[J]. RSC Advances, 2017, 7(31): 18926-18936.
40	JIAO X Y, HAO Q L, LIU P, et al. Facile synthesis of T-Nb₂O₅ nanosheets/nitrogen and sulfur co-doped graphene for high performance lithium-ion hybrid supercapacitors[J]. Science China Materials, 2018, 61(2): 273-284.
41	YUAN T, TAN Z P, MA C R, et al. Challenges of spinel Li₄Ti₅O₁₂ for lithium-ion battery industrial applications[J]. Advanced Energy Materials, 2017, 7(12): 1601625.
42	LENG K, ZHANG F, ZHANG L, et al. Graphene-based Li-ion hybrid supercapacitors with ultrahigh performance[J]. Nano Research, 2013, 6(8): 581-592.
43	AJURIA J, ARNAIZ M, BOTAS C, et al. Graphene-based lithium ion capacitor with high gravimetric energy and power densities[J]. Journal of Power Sources, 2017, 363: 422-427.
44	VELMURUGAN V, SRINIVASARAO U, RAMACHANDRAN R, et al. Synthesis of Tin oxide/graphene (SnO₂/G) nanocomposite and its electrochemical properties for supercapacitor applications[J]. Materials Research Bulletin, 2016, 84: 145-151.
45	KIM H K, ARAVINDAN V, ROH M H K, et al. Exploring high-energy Li-ion batteries and capacitors with conversion-type Fe₃O₄-RGO as the negative electrode[J]. ChemElectroChem, 2017, 4(10): 2626-2633.
46	ZHANG S, LI C, ZHANG X, et al. High performance lithium-ion hybrid capacitors employing Fe₃O₄-graphene composite anode and activated carbon cathode[J]. ACS Applied Materials Interfaces, 2017, 9(20): 17136-17144.
47	ZHAO X R, ZHANG X, LI C, et al. High-performance lithium-ion capacitors based on CoO-graphene composite anode and holey carbon nanolayer cathode[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(13): 11275-11283.
48	赵兴茹, 安琪, 马向东, 等. 金属氧化物作为锂离子电容器负极的研究进展[J]. 储能科学与技术, 2018, 7(4): 555-564.
	ZHAO X R, AN Q, MA X D, et al. Research progress of metal oxides as anodes for lithium ion capacitor[J]. Energy Storage Science and Technology, 2018, 7(4): 555-564.

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