烯碳材料用于锌离子混合电容器的研究进展

ZHOU Yi-jing; LUO Jin-rong; SHAO Yan-yan; XIA Zhou; SHAO Yuan-long

doi:10.1016/S1872-5805(22)60642-5

烯碳材料用于锌离子混合电容器的研究进展

doi: 10.1016/S1872-5805(22)60642-5

周伊静¹,
罗金荣¹,
邵妍妍¹,
夏洲¹,
邵元龙^{1, 2, 3, ,}

1.
苏州大学能源学院苏州能源与材料创新研究所，苏州大学先进碳材料与可穿戴能源技术重点实验室，江苏苏州 215006
2.
北京大学材料科学与工程学院，北京 100871
3.
北京石墨烯研究院，北京 100871

基金项目: 国家自然科学基金项目（52003188），国家自然科学基金基础科学中心项目（T2188101），江苏省自然科学基金项目（BK20200871），江苏省创新创业人才计划（JSSCRC2021529），姑苏青年领军人才（ZXL2021449），苏州市重点产业技术创新项目（SYG202108）

详细信息

通讯作者:
邵元龙，研究员. E-mail：shaoyuanlong@pku.edu.cn

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2022-06-27
- 修回日期: 2022-08-29
- 网络出版日期: 2022-08-23
- 刊出日期: 2022-10-01

Progress on carbonene-based materials for Zn-ion hybrid supercapacitors

1.
College of Energy, Soochow Institute for Energy and Materials Innovations (SIEMIS), Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies, Soochow University, Suzhou 215006, China
2.
School of Materials Science and Engineering, Peking University, Beijing 100871, China
3.
Beijing Graphene Institute (BGI), Beijing 100095, China

Funds: This project was financially supported by National Natural Science Foundation of China (52003188 (Y.S.)), Natural Science Foundation of Jiangsu Province (BK20200871 (Y.S.)), Jiangsu innovation and entrepreneurship talent program (JSSCRC2021529), Gusu's young leading talent (ZXL2021449), Key industry technology innovation project of Suzhou (SYG202108)

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Author Bio:
^†周伊静、罗金荣为共同第一作者

Corresponding author: SHAO Yuan-long，Professor. E-mail: shaoyuanlong@pku.edu.cn

摘要

摘要: 随着可穿戴电子设备的出现，诸如锌离子混合电容器等绿色储能器件，因其具有安全性高、稳定性好、成本低、功率密度高、能量密度大的特点，从而受到了广泛的关注。对于锌离子混合电容器，烯碳材料（主要包括石墨烯和碳纳米管）由于其卓越的导电性和良好的机械稳定性，被认为是一种十分有前景的材料。在此，作者对用于锌离子混合电容器的烯碳基材料的改性策略进行了全面的综述，并对锌离子混合电容器的储能机理、锌阳极和电解液进行了简要总结。最后，还对锌离子混合电容器的未来研究方向进行了展望。
- 锌离子混合电容器 /
- 烯碳材料 /
- 碳纳米管 /
- 石墨烯
Abstract: Along with the emergence of wearable electronic devices, green energy devices like Zn-ion hybrid supercapacitors (ZHSCs), which are extremely safe and cheap, and have excellent stability and high power energy densities, have received great attention. Carbonenes, mainly including graphene and carbon nanotubes (CNTs), are promising materials for ZHSCs because of their exceptional electrical conductivity and excellent mechanical stability. A comprehensive overview of strategies for the modification of carbonene-based materials for ZHSCs, and a brief summary of their energy storage mechanisms is given and topics for potential research are suggested.
- Zn-ion hybrid supercapacitors /
- Carbonene materials /
- Carbon nanotubes /
- Graphene

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FIG. 1816. FIG. 1816.

FIG. 1816.. FIG. 1816.

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Figure 1. Common carbon-based cathode materials, including PC-based materials^[23], HCS-based materials^[26], graphene-based materials^{[31, 32]} and CNT-based materials^[29]. And varied strategies for designing high-performance ZHSCs, including porosity engineering, structure design, heteroatom doping and introduction conductive additives.

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Figure 2. (a) Diagrams of fabrication process of ZmSCs. (b) Morphology of untreated CNTs paper^[14]. (c) Synthesis process of N-CNT@CNT fiber electrode. (d) SEM image of original CNTs fiber^[29]. (Reprinted with permission)

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Figure 3. (a) Morphology of ZFO powders. (b) Morphology of AC/MWNTs/ZFO compounds. (c) The cyclic voltammetry curves of ZFO, MWNTs, AC and AC/MWNTs/ZFO compounds in 3 mol L⁻¹ KOH electrolyte^[46]. (d) Synthesis process of DV₂C@CNT film with laminated structure. (e) Cycling stability of DV₂C@CNT self-supporting electrode under 0.5 A·g⁻¹^[30]. (Reprinted with permission)

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Figure 4. (a) Preparation procedure of rGO/CNT and graphite fibers@Zn and the diagrams of fabrication process of assembling fiber-shaped ZHSCs and its working mechanism. (b) CV curves of the fiber-shaped ZHSCs-PAA when bent at different angles. (c) Comparison of thus-prepared fiber-shaped ZHSCs with recently reported various fiber-shaped capacitors^[28]. MWNTs-rGO fibers’ SEM images in (d) winded and (e) knotted mode. (f) Digital photograph of the fiber-shaped ZHSCs under bending state^[47]. (g) Normalized capacitance as a function of stretch times, inset is CV curves of capacitor with CNT−rGO@F electrode after stretching and releasing for several times. (h) Comparison of the conductivity variation between rGO@F and CNT−rGO@F during one period of exerting 50% strain and releasing. (i) Digital image of the CNT−rGO@F compound^[48]. (Reprinted with permission)

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Figure 5. (a) The cross-sectional morphology of GH films with varied treatment time. (b) Cycling performance of the ZHSCs. (c) Optical photograph and SEM image of GH films^[61]. (d) The reasons for PQ-GH material with excellent performances^[27]. (e) Preparation diagrams of NHG-GO films from GO and NHG dispersions^[64]. (Reprinted with permission)

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Figure 6. (a) SEM image of 3D graphene hydrogel. (b) Cycling performance at the current density of 10 A·g⁻¹. (c) Display diagrams of two devices in series lighting pattern “LZ”^[67]. (d) Preparation flowchart of 3DVAG. (e) Microscopic morphology of graphene gel obtained from hydrothermal. (f) Comparison of rate performance with 3DrGO^[68]. (Reprinted with permission)

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Figure 7. (a) The illustration for preparation of NPG nano-compounds. (b) Morphology of NPG-0.75 power. (c) The long-term cycling lifespan at current density of 5 A·g⁻¹ (inset is corresponding GCD curves)^[75]. (d) LED bulb and the timing device in parallel were lighted by independent ZHSCs^[31]. (e) Diagrams of working mechanism of ZHSCs, stressing the importances of oxygen-containing groups in elevating pseudocapacitance. (f) Rate capability of rGO films obtained from various treatments. (g) The CV curve of quasi-solid-state ZHSCs measured at different bending angles (ranging from 0° to 90°)^[76]. (Reprinted with permission)

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Figure 8. (a) Preparation of MXene-rGO aerogels. (b) Mechanical properties of MXene-rGO aerogel. (c) Elemental analysis images of MXene-rGO aerogel^[77]. (d) and (e) SEM images of PPy/EGO-1200 s powders. (f) Comparison of rate performance of PPy/EGO under varied deposition conditions^[79]. (Reprinted with permission)

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Table 1. Electrochemical performance summary of CNT-based materials for ZHSCs.

Cathode	Anode	Electrolyte	Potential (V)	Specific capacity	Energy density	Power density	Cycle performance	Ref.
CNTs	Zn	1 M ZnSO₄	0-1.8	20 mF·cm⁻² (10 mV·s⁻¹)	/	/	~100% 5000 cycles (500 mV·s⁻¹)	[44]
CNT	Recoverable Zn	1 M ZnSO₄	0.2-1.8	83.2 mF·cm⁻² (1 mA·cm^{− 2})	29.6 μWh·cm⁻²	8 mW·cm⁻²	87.4% 6000 cycles (5 mA·cm⁻²)	[14]
N-CNT @CNT	Zn@CNT fiber	3 M Zn(CF₃SO₃)₂/ PVA gel	0-1.8	11.52 mF·cm⁻² ( 0.71 mA·cm⁻²)	5.18 mW·h cm⁻²	3.23 mW·cm⁻²	88.56% 10000 cycles (1.42 mA·cm⁻²)	[29]
V2C MXene @CNT	Zn foil	1 M ZnSO₄	0.1-1.1	190.2 F·g⁻¹ (0.5 A·g⁻¹)	/	/	/	[30]
rGO/CNT	Zn-coated graphite	ZnSO₄-filled PAA hydrogel	0-1.8	76.7 F·cm⁻³, at (8000 mA·cm⁻³)	48.5 mWh·cm⁻³	179.9 mW·cm⁻³	98.5% 10000 cycles (3200 mA·cm⁻³)	[28]
MWCNTs-rGO	MWCNTs-rGO-Zn	Zn(CF₃SO₃)₂ / PVA gel	0-1.8	41.2 F·cm⁻³ (1 mV·s⁻¹)	13.1 mWh·cm⁻³	1433.2 mW·cm⁻³	~100% 4000 cycles (1.5924 A·cm⁻³)	[47]
Activated carbon	Zn@CNTS	2 M Zn(CF₃SO₃)₂	0.2-1.8	77 mAh·g⁻¹ (0.1 A·g⁻¹)	/	/	~100% 7000 cycles (2 A·g⁻¹)	[49]
3DP MXene	Zn@3DP CNT	2 M ZnSO₄	0.1-1.2	184.4 F·g⁻¹ (10 A·g⁻¹)	0.10 mWh·cm⁻²	5.90 mW·cm⁻²	86.5% 6000 cycles (10 mA·cm⁻²)	[50]
Note: M: mol L⁻¹

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Table 2. Electrochemical performance summary of graphene-based materials for ZHSCs.

Cathode	Anode	Electrolyte	Potential (V)	Specific capacity	Energy density	Power density	Cycle performance	Ref.
aMEGO	Zn	3 M Zn(CF₃SO₃)₂	0-1.9	/	106.3 Wh·kg⁻¹	31.4 kW·kg⁻¹	93% 80000 cycles (8 A·g⁻¹)	[15]
GO	Zn	2 M ZnSO₄	0.2-1.8	60 mAh·g⁻¹ (10 A·g⁻¹)	52.2 Wh·kg⁻¹	3602 W·kg⁻¹	~90% 10000 cycles (15 A·g⁻¹)	[61]
rGO@PPD	Zn foil	1 M Zn(Ac)₂	0.2-1.8	3.012 F·cm⁻² (1 mA·cm⁻²)	1.1 mWh·cm⁻²	0.8 mW·cm⁻²	~100% 4000 cycles (7 mA·cm^{− 2})	[62]
N-rGO/PPy	Zn	2 M ZnSO₄	0-1.6	145.32 mAh·g⁻¹ (0.1 A·g⁻¹)	232.50 Wh·kg⁻¹	160 W·kg⁻¹	85% 10000 cycles (7.0 A·g⁻¹)	[63]
PQ-FGH	Zn foil	1 M ZnSO₄	0.2-1.8	/	32.6 mW·cm⁻²	1.31 mWh·cm⁻²	/	[27]
NHG-rGO	Zn foil	2 M ZnCl₂	0.2-1.7	235.4 μF·cm⁻³ (0.1 A·g⁻¹)	73.6 Wh·kg⁻¹	75.2 W·kg⁻¹	93.9% 100000 cycles (5 A·g⁻¹)	[64]
DGH	Zn foil	1 m ZnSO₄	0.2-1.8	222.03 F·g⁻¹ (0.5 A·g⁻¹)	118.42 Wh·L⁻¹	24.00 kW·L⁻¹	80% 30000 cycles (10 A·g⁻¹)	[67]
3DVAG	Zn flake	2 M ZnSO₄	0.2-1.7	44.4 F·g⁻¹ (0.3 A·g⁻¹)	17.03 Wh·kg⁻¹	249.3 W·kg⁻¹	94.6% 3000 cycles (2 A·g⁻¹)	[68]
PDA@3DVAG	Activated carbon	18 M ZnCl₄ + 6 M NH₄Cl	-0.8-0.8	133.9 F·g⁻¹ (0.5 A·g⁻¹)	46.14 Wh·kg⁻¹	2183 W·kg⁻¹	61.8% 3000 cycles (1 A·g⁻¹)	[32]
NPG	Zinc foil	1 M ZnSO₄	0-1.8	210.2 F·g⁻¹ (0.5 A·g⁻¹)	94.6 Wh·kg⁻¹	4500 W·kg⁻¹	82% 15000 cycles (10 A·g⁻¹)	[75]
N/P-doped rGO	Zn foil	1 M Zn(Ac)₂ and 20 M KAc hydrogel	0-2.0	/	106.5 Wh·kg⁻¹	383.3 W·kg⁻¹	86.6% 8000 cycles (5 A·g⁻¹)	[31]
HHT-rGO	Zn	1 M ZnSO₄	0.2-1.6	159 F·g⁻¹ (100 mV·s⁻¹)	342 μWh·cm⁻²	880 mW·cm⁻²	97.8% 20000 cycles (2.5 A·g⁻¹)	[76]
MXene-rGO aerogel	Zn foil	2 M ZnSO₄	0.2-1.6	128.6 F·g⁻¹ (0.4 A·g⁻¹)	34.9 Wh·kg⁻¹	279.9 W·kg⁻¹	95% 75000 cycles (5 A·g⁻¹)	[77]
Porous carbon	Zn@CoNiP/rGO	2 M ZnSO₄	0.2-1.9	356.6 F·g⁻¹ (0.5 A·g⁻¹)	143.14 Wh·kg⁻¹	425 W·kg⁻¹	92.2% 10000 cycles (7.5 A·g⁻¹)	[78]
PPy/EGO	Zn foil	1 M ZnCl₂	0.5-1.5	633.0 mF·cm⁻² (0.5 mA·cm⁻²)	117.7 Wh·kg⁻¹	12.4 kW·kg⁻¹	81% 5000 cycles (5 mA·cm⁻²)	[79]
Note: M: mol L⁻¹

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