石墨烯在平面微型超级电容器中的应用进展与展望

LI Hu-cheng; SHEN Hao-rui; SHI Ying; WEN Lei; LI Feng

doi:10.1016/S1872-5805(22)60640-1

石墨烯在平面微型超级电容器中的应用进展与展望

doi: 10.1016/S1872-5805(22)60640-1

李虎成^{1, 2,},
申浩瑞^{1, 2},
石颖^{1, 2},
闻雷^{1, 2, ,},
李峰^{1, 2, 3, ,}

1.
中国科学院金属研究所沈阳材料科学国家研究中心，辽宁沈阳 110016
2.
中国科学技术大学材料科学与工程学院，辽宁沈阳 110016
3.
中国医科大学生物化学与分子生物学教研室，辽宁沈阳 110122

基金项目: 国家自然科学基金项目(51927803，51902316)；国家重点研发计划项目(2016YFA0200102，2016YFB0100100)；辽宁省“兴辽英才计划”项目(XLYC1908015)

详细信息

通讯作者:
闻　雷，副研究员. E-mail：leiwen@imr.ac.cn

李　峰，研究员. E-mail：fli@imr.ac.cn

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2022-06-29
- 修回日期: 2022-08-12
- 网络出版日期: 2022-08-15
- 刊出日期: 2022-10-01

Progress and prospects of graphene for in-plane micro-supercapacitors

LI Hu-cheng^{1, 2
,},
SHEN Hao-rui^{1, 2},
SHI Ying^{1, 2},
WEN Lei^{1, 2
, ,},
LI Feng^{1, 2, 3
, ,}

1.
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2.
School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3.
Department of Biochemistry and Molecular Biology, College of Life Science, China Medical University, Shenyang 110122, China

Funds: The authors acknowledge financial support from National Natural Science Foundation of China (51927803 and 51902316), National Key R&D Program of China (2016YFA0200102 and 2016YFB0100100) and LiaoNing Revitalization Talents Program (XLYC1908015)

More Information

Author Bio:
李虎成，博士研究生. E-mail：hcli16s@imr.ac.cn

Corresponding author: WEN Lei, Associate professor. E-mail: leiwen@imr.ac.cn; LI Feng, Professor. E-mail: fli@imr.ac.cn

摘要

摘要: 微型超级电容器具有高功率密度和长循环寿命，有望为物联网设备供电。然而，较低的能量密度阻碍了微型超级电容器的实际应用。电极材料是影响微型超级电容器性能的一个重要因素。石墨烯由于具有比表面积大和导电性高等优势，是微型超级电容器的理想电极材料。当石墨烯用于具有平面构型的微型超级电容器时，其二维表面与电解质离子的传输方向平行，有利于提高电极的离子可及性。因此，构建石墨烯基平面微型超级电容器，引起了研究人员的极大兴趣。本文从电极材料设计的角度，总结了平面微型超级电容器用石墨烯和石墨烯基材料的最新研究进展。这些电极材料包括通过化学气相沉积、液相剥离、氧化石墨烯还原、激光诱导和杂原子掺杂方法获得的石墨烯，及石墨烯基复合材料（碳纳米管/石墨烯、过渡金属氧化物/石墨烯、导电聚合物/石墨烯和二维材料/石墨烯）。讨论了石墨烯基平面微型超级电容器面临的挑战和机遇，并展望了未来的研究方向和发展趋势。
- 石墨烯 /
- 微型超级电容器 /
- 电极材料 /
- 能量储存
Abstract: Micro-supercapacitors hold great promise for powering the Internet of Things devices owing to their high power density and long cycling life. However, the limited energy density hinders their practical use. Electrode materials play an important role in the performance of micro-supercapacitors. With the advantages of a large specific surface area and a high electrical conductivity, graphene has been considered a good candidate for the electrode material of micro-supercapacitors. The two-dimensional surface of graphene is parallel to the direction of transport of the electrolyte ions for micro-supercapacitors with an in-plane structure, which helps improve the ion accessibility of the electrodes. Therefore, the construction of graphene-based in-plane micro-supercapacitors has aroused great interest among researchers. Here, we summarize the recent advances in graphene and graphene-based materials for in-plane micro-supercapacitors from the perspective of electrode material design. The electrode materials include graphenes produced by chemical vapor deposition, liquid-phase exfoliation, reduction of graphene oxide, laser induction and heteroatom doping, as well as graphene-based composites, such as carbon nanotube/graphene, transition metal oxide/graphene, conducting polymer/graphene and two-dimensional material/graphene composites. Challenges and opportunities in graphene-based in-plane micro-supercapacitors are discussed, and future research directions and development trends are proposed.
- Graphene /
- Micro-supercapacitor /
- Electrode material /
- Energy storage

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FIG. 1810. FIG. 1810.

FIG. 1810.. FIG. 1810.

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Figure 1. Schematic illustration of the electrolyte ion transport for in-plane micro-supercapacitors with the graphene electrode.

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Figure 2. Schematic illustration of graphene and graphene-based materials for in-plane micro-supercapacitors.

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Figure 3. Schematic illustration of micro-supercapacitors with (a) stacked and (b) in-plane architectures.

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Figure 4. Schematic illustration of the fabrication of micro-supercapacitors using technologies based on powder materials or film materials.

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Figure 5. (a) Schematic illustration of the fabrication of multilayer graphene (MG) films for micro-supercapacitors (MSCs). (b) Photo of micro-supercapacitors with various geometries on PET substrate. (c) Magnified photo corresponding to (b). (d) Cyclic voltammetry (CV) curves of micro-supercapacitors at 10 V s⁻¹^[34]. Reprinted with permission.

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Figure 6. (a) Photo of EG ink (left) and H₃PO₄/PSSH ink (right). (b) Photo of printed micro-supercapacitors on the glass slide substrate. (c) Scanning electron microscope (SEM) image of EG electrodes. (d) Photo showing the large-scale integration of over 100 micro-supercapacitors on the PI substrate. (e) CV curves of integrated micro-supercapacitors^[23]. Reprinted with permission.

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Figure 7. (a) Schematic illustration of the fabrication of micro-supercapacitors with the rGO electrode. (b) Photo showing over 100 micro-supercapacitors produced on a single disc. (c) Magnified photo corresponding to (b). (d) GCD curves of micro-supercapacitors^[45]. Reprinted with permission.

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Figure 8. (a) Schematic illustration of the fabrication of LIG from PI. (b) SEM image of the LIG film, inset is the corresponding magnified image. (c) Cross-sectional SEM image of the LIG film, inset is the corresponding magnified image. (d) AC-STEM image of LIG. (e) CV curves and (f) GCD curves of micro-supercapacitors with the LIG electrode^[33]. Reprinted with permission.

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Figure 9. (a) Schematic illustration of the fabrication of S-doped graphene films for micro-supercapacitors. (b) CV curves of micro-supercapacitors^[37]. Reprinted with permission.

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Figure 10. (a) Schematic illustration of the fabrication of EG by wet-jet milling exfoliation of graphite. (b) Addition of SWCNTs as spacers between EG. (c) Cross-sectional SEM image of the SWCNT/EG electrode^[83]. Reprinted with permission.

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Figure 11. (a) Schematic illustration of the laser fabrication of V₈C₇/rGO films. (b) Photo of over 20 micro-supercapacitors obtained by laser scribing. (c) Cross-sectional SEM image of V₈C₇/rGO electrodes. (d) Transmission electron microscope image of V₈C₇/rGO electrodes^[91]. Reprinted with permission.

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Figure 12. (a) Schematic illustration of the fabrication of 2D polymers with cylindrical mesopores on rGO nanosheets via an interfacial self-assembly approach. (b) Schematic illustration of cylindrical mesopores parallel to the graphene for facilitating ion transport. (c) Areal and volumetric capacitances of micro-supercapacitors with the PPy/rGO electrode^[95]. Reprinted with permission.

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Figure 13. (a) Schematic illustration of the fabrication of micro-supercapacitors with the phosphorene/EG electrode by mask-assisted filtration. Photos of 9 serially interconnected micro-supercapacitors (b) in a flat state and (c) in a folded state. The inset of (c) corresponds to the recovered state^[27]. Reprinted with permission.

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Figure 14. Schematic illustration of the prospects of graphene-based micro-supercapacitors

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Table 1. Performance of typical graphene materials for micro-supercapacitors^a.

Electrode material	Fabrication technology	Electrode thickness	Electrolyte	Operating voltage (V)	Areal capacitance (mF cm⁻²)	Volumetric capacitance (F cm⁻³)	Energy density (mWh cm⁻³)	Power density (W cm⁻³)	Refs.
Graphene by CVD	Blade cutting	N/A	H₃PO₄/PVA	1.0	0.1	N/A	N/A	N/A	[15]
Graphene by CVD	Laser scribing	17 nm	EMIMTFSI/fumed silica	2.5	<0.1	26.5	23.0	1860.0	[34]
Graphene by CVD	Photolithography	5 nm	H₂SO₄/PVA	1.0	0.1	131.0	18.2	N/A	[40]
Graphene by CVD	Plasma etching	5 nm	H₂SO₄/PVA	1.0	0.2	307.0	42.6	2000.0	[41]
EG	Inkjet printing	N/A	Na₂SO₄	0.7	0.6	N/A	N/A	N/A	[42]
EG	Spray coating	500 nm	H₂SO₄/PVA	1.0	0.8	16.0	2.2	N/A	[20]
EG	Inkjet printing	750 nm	H₃PO₄/PSSH	1.0	0.7	9.3	1.3	0.6	[23]
EG	Stamping	58 μm	H₂SO₄/PVA	1.0	4.0	0.7	0.1	0.1	[43]
EG	Mask-assisted filtration	600 nm	KTFSI-P₁₄TFSI/PVDF-HFP	3.4	0.5	9.0	14.5	2.6	[44]
rGO	Laser scribing	2 μm	GO films with trapped water	1.0	0.5	3.1	0.4	9.4	[32]
rGO	Laser scribing	8 μm	BMIMNTF₂/fumed silica	2.5	1.9	2.4	2.0	200.0	[45]
rGO	Plasma reduction and plasma etching	15 nm	H₂SO₄/ PVA	1.0	0.1	17.9	2.5	495.0	[46]
rGO	Laser scribing	50 μm	H₃PO₄/PVA	0.8	15.3	3.1	0.3	N/A	[47]
rGO	Direct heating	200 μm	H₂SO₄/PVA	1.0	94.8	4.7	0.7	N/A	[48]
LIG	Laser scribing	25 μm	H₂SO₄	1.0	4.0	1.6	0.4	50.0	[33]
LIG	Laser scribing	82 μm	H₃PO₄/PVA	0.8	0.6	0.1	<0.1	<0.1	[49]
LIG	Laser scribing	39 μm	H₂SO₄/PVA	1.0	25.1	6.5	1.0	2.0	[50]
LIG	Laser scribing	90 μm	H₂SO₄/PVA	1.0	35.3	3.9	0.1	<0.1	[51]
B-doped graphene	Laser scribing	25 μm	H₂SO₄/PVA	1.0	16.5	6.6	0.6	3.5	[52]
S-doped graphene	Plasma etching	10 nm	H₂SO₄/PVA	1.0	0.1	22.3	3.1	1191.0	[37]
F-doped graphene	Mask-assisted filtration	1 μm	EMIMBF₄/PVDF-HFP	3.5	17.4	134.0	56.0	21.0	[53]
Cl-doped graphene	Mask-assisted filtration	500 nm	EMIMBF₄/PVDF-HFP	3.5	8.0	160.0	97.9	38.5	[54]
N/O co-doped graphene	3D printing	100 μm	H₃PO₄/PVA	1.0	18.7	1.9	0.3	<0.1	[55]
^aNote: N/A, not available; PVA, poly(vinyl alcohol); PSSH, poly(4-styrenesulfonic acid); EMIMTFSI, 1-ethyl-3-methyl-imidazolium-bis (trifluoromethylsulfonyl) imide; KTFSI-P₁₄TFSI, potassium bis(tri-ﬂuoromethanesulfonyl)imide in 1-butyl-1-methylpyrrolidinium bis(tri-ﬂuoromethanesulfonyl)imide; PVDF-HFP, poly(vinylidene ﬂuoride-hexaﬂuoropropylene); BMIMNTF₂, 1-butyl-3-methylimidazolium bis(triﬂuoromethylsulfonyl)imide; EMIMBF₄, 1-ethyl-3-methylimidazolium tetraﬂuoroborate. Electrochemical performance data are based on the device and obtained or estimated from the best results in the literature.

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Table 2. Performance of typical graphene-based materials for micro-supercapacitors^a.

Electrode material	Fabrication technology	Thickness	Electrolyte	Operating voltage (V)	Areal capacitance (mF cm⁻²)	Volumetric capacitance (F cm⁻³)	Energy density (mWh cm⁻³)	Power density (W cm⁻³)	Refs.
MWCNT/EG	Spray coating	6 μm	KCl	1.0	5.6	4.9	0.7	77.0	[82]
SWCNT/EG	Screen printing	27 μm	H₃PO₄/PVA	1.8	1.3	0.5	0.2	7.4	[83]
MWCNT/rGO	Continuous centrifugal coating and HI reduction	1 μm	H₂SO₄/PVA	0.8	1.6	16.1	1.4	0.2	[84]
RuO₂/rGO	Laser scribing	11 μm	H₂SO₄	1.0	34.1	31.9	4.4	12.4	[85]
MnO₂/rGO	Laser scribing	15 μm	Na₂SO₄	0.9	400.0	250.0	30.0	8.0	[86]
MnO₂/LIG	Laser scribing and electrolytic deposition	101 μm	LiCl/PVA	1.0	934.0	93.4	3.2	0.3	[30]
MnO₂/rGO	Spatially shaped femtosecond laser	3 μm	Na₂SO₄	2.0	128.0	426.7	230.0	136.0	[87]
ZnO/rGO	Laser scribing and hydrothermal reaction	11 μm	H₂SO₄/PVA	1.0	4.3	3.9	0.4	0.4	[88]
V₂O₅/EG	Plasma etching	300 nm	LiCl/PVA	1.0	3.9	130.7	20.0	235.0	[89]
VO_x/rGO	3D printing	412 μm	LiCl/PVA	1.0	133.2	3.2	0.5	<0.1	[90]
V₈C₇/rGO	Continuous centrifugal coating and laser scribing	13 μm	LiCl/PVA	0.8	49.5	38.1	3.4	0.4	[91]
PANI/rGO	Plasma etching	5 μm	H₂SO₄/PVA	1.0	210.0	436.0	11.7	2.0	[92]
PANI/GO	Extrusion printing	80 μm	H₃PO₄/PVA	0.8	153.6	19.2	1.9	0.8	[93]
PPy/GO	Plasma etching	2 μm	H₂SO₄/PVA	1.0	0.1	0.5	N/A	N/A	[94]
PPy/rGO	Mask-assisted filtration	7 μm	H₂SO₄/PVA	0.8	81.0	102.0	2.3	0.5	[95]
PPy/rGO	Mask-assisted filtration	3 μm	H₂SO₄/PVA	0.8	38.0	110.0	2.5	0.4	[96]
Th/EG	Plasma etching	105 nm	H₂SO₄/PVA	1.0	3.9	375.0	13.0	776.0	[97]
MXene/rGO	Laser scribing	N/A	H₂SO₄/PVA	0.6	34.6	N/A	N/A	N/A	[98]
Phosphorene/EG	Mask-assisted filtration	2 μm	BMIMPF₆	3.0	9.8	37.0	11.6	1.5	[27]
^aNote: MWCNT, multi-walled carbon nanotubes; SWCNT, single-walled carbon nanotubes; PANI, polyaniline; PPy, polypyrrole; Th, Thiophene; BMIMPF₆, 1-butyl-3-methylimidazolium hexaﬂuorophosphate. Electrochemical performance data are based on the device and obtained or estimated from the best results in the literature.

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