高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (2): 539.doi: 10.7503/cjcu20200579
陈明华(), 李宏武, 范鹤, 李誉, 刘威铎, 夏新辉, 陈庆国
收稿日期:
2020-08-20
出版日期:
2021-02-10
发布日期:
2020-12-17
通讯作者:
陈明华
E-mail:mhchen@hrbust.edu.cn
基金资助:
CHEN Minghua(), LI Hongwu, FAN He, LI Yu, LIU Weiduo, XIA Xinhui, CHEN Qingguo
Received:
2020-08-20
Online:
2021-02-10
Published:
2020-12-17
Contact:
CHEN Minghua
E-mail:mhchen@hrbust.edu.cn
Supported by:
摘要:
近年来, 过渡金属硫族化合物(TMDs)作为一种新兴的二维材料, 因其独特的层状结构及电学特性成为超级电容器电极材料的理想候选者之一. 本文介绍了二维TMDs的常用合成方法, 阐述了钼基、 钨基和钒基等TMDs在超级电容器中的研究进展, 分析了形貌、 尺寸和改性方法等因素对TMDs材料电化学性能的影响, 并对TMDs在超级电容器领域的工业化应用和挑战进行了总结与展望.
中图分类号:
TrendMD:
陈明华, 李宏武, 范鹤, 李誉, 刘威铎, 夏新辉, 陈庆国. 二维过渡金属硫族化合物在超级电容器中的研究进展. 高等学校化学学报, 2021, 42(2): 539.
CHEN Minghua, LI Hongwu, FAN He, LI Yu, LIU Weiduo, XIA Xinhui, CHEN Qingguo. Research Progress of Two-dimensional Transition Metal Dichalcogenides in Supercapacitors. Chem. J. Chinese Universities, 2021, 42(2): 539.
Fig.2 Schematic diagram of common stripping methods(A) Mechanical stripping; (B) sonication-assiste stripping; (C) ion intercalation assisted liquid phase stripping.
Fig.4 Other TMDs preparation methods(A) Preparation of MoS2@C nanofibers by electrospinning technology[73], Copyright 2017, Elsevier B.V.; (B) preparation of porous MoS2 by sol-gel method[74], Copyright 2012, Elsevier B.V.; (C) Laser thinning diagram[75], Copyright 2012, American Chemical Society.
Synthesis method | Advantage | Drawback |
---|---|---|
Exfoliation method | High yield and simple operation | Uncontrollable product morphology and layer number |
CVD | Good crystallinity, controllable number of layers | Low yield, high cost, high reaction temperature |
Hydro/Solvothermal method | Large number of active sites, low cost | Poor crystallinity |
Electrospinning | Low cost, forming soft flexible thin film | Low efficiency |
Sol?gel method | High purity, high porosity | Longer period, high cost |
MBE and ALD | Easy and precise control | Slow growth rate, high equipment cost and requirement |
Table 1 Preparation methods of 2D TMDs
Synthesis method | Advantage | Drawback |
---|---|---|
Exfoliation method | High yield and simple operation | Uncontrollable product morphology and layer number |
CVD | Good crystallinity, controllable number of layers | Low yield, high cost, high reaction temperature |
Hydro/Solvothermal method | Large number of active sites, low cost | Poor crystallinity |
Electrospinning | Low cost, forming soft flexible thin film | Low efficiency |
Sol?gel method | High purity, high porosity | Longer period, high cost |
MBE and ALD | Easy and precise control | Slow growth rate, high equipment cost and requirement |
Fig.6 Schematic atomic model of the MoS2/G nanohybrid(A), relative fractions of 2H and 1T components as a function of annealing temperatures(B) and the experimental capacitance of graphene film(C)[92]MoS2/G, MoS2 film and calculated capacitance of MoS2 as a function of annealing temperatures are summarized.Copyright 2019, Wiley.
Fig.7 H+ ion storage of 1T?MoS2 or Ti3C2 MXene and extra H+ ion storage in 1T-MoS2/Ti3C2 MXene heterostucture at charged?discharged state(A), digital photographs and values of L and R of flexible 1T?MoS2/Ti3C2 MXene based flexible all?solid?state supercapacitor(ASSS) bended at different angles(B), CV curves of the ASSS device bended at different angles at 30 mV/s(C) and photographs of the three ASSS devices connected in series driving electronic watch(D)[93]Copyright 2020, Wiley-VCH.
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
Flower shape MoS2 | 1 mol/L Na2SO4 | 92.8 F/g(0.5 mA/cm2) | 93.8%(1000 cycles) | [ |
MoS2 film | 0.5 mol/L H2SO4 | ca. 330 F/cm3(25.47 mA/cm2) | 97%(5000 cycles) | [ |
MoS2/rGO | 1 mol/L Na2SO4 | 250%(10000 cycles) | [ | |
MoS2/rGO@PANI | 1 mol/L H2SO4 | 1224 F/g(1 A/g) | 82.5%(3000 cycles) | [ |
CoS@MoS2 Nanowires | 2 mol/L KOH | 1687.7 F/g(4 mA/cm2) | 96.2%(10000 cycles) | [ |
1T?MoS2/PVAK+ | 3 mol/L KCl | 448 F/g(1 A/g) | 96%(16000 cycles) | [ |
1T?2H MoS2/rGO | 1 mol/L H2SO4 | 416 F/g(1 A/g) | 50000 cycles | [ |
MoS2/Graphene | 6 mol/L KOH | 272 F/g | [ | |
1T?MoS2/Ti3C2 | 1 mol/L H2SO4 | 386.7 F/g(1 A/g) | 96.8%(20000 cycles) | [ |
MoSe2/MoS2 | 0.5 mol/L H2SO4 | 1229.6 F/g(1 A/g) | 92.8%(2000 cycles) | [ |
MoS2/CNT | 1 mol/L Na2SO4 | 337 mF/cm2 | 97.6%(2500 cycles) | [ |
MoSe2/Ni foam | 6 mol/L KOH | 1114.1 F/g(1 A/g) | 104.7%(1500 cycles) | [ |
Flake MoSe2 | 1 mol/L Na2SO4 | 1467.8 F/g(4 mA/cm2) | 80%(1000 cycles) | [ |
MoSe2/rGO | 6 mol/L KOH | 1422 F/g(1 A/g) | 100.7%(1500 cycles) | [ |
MoSe2/Acetylene black | 6 mol/L KOH | 2020 F/g(1 A/g) | 107.5%(1500 cycles) | [ |
1T’?MoSe2@rGO | — | 1791 F/g(1 A/g) | 98.6%(2000 cycles) | [ |
Table 2 Molybdenum-based TMDs supercapacitor performance comparison
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
Flower shape MoS2 | 1 mol/L Na2SO4 | 92.8 F/g(0.5 mA/cm2) | 93.8%(1000 cycles) | [ |
MoS2 film | 0.5 mol/L H2SO4 | ca. 330 F/cm3(25.47 mA/cm2) | 97%(5000 cycles) | [ |
MoS2/rGO | 1 mol/L Na2SO4 | 250%(10000 cycles) | [ | |
MoS2/rGO@PANI | 1 mol/L H2SO4 | 1224 F/g(1 A/g) | 82.5%(3000 cycles) | [ |
CoS@MoS2 Nanowires | 2 mol/L KOH | 1687.7 F/g(4 mA/cm2) | 96.2%(10000 cycles) | [ |
1T?MoS2/PVAK+ | 3 mol/L KCl | 448 F/g(1 A/g) | 96%(16000 cycles) | [ |
1T?2H MoS2/rGO | 1 mol/L H2SO4 | 416 F/g(1 A/g) | 50000 cycles | [ |
MoS2/Graphene | 6 mol/L KOH | 272 F/g | [ | |
1T?MoS2/Ti3C2 | 1 mol/L H2SO4 | 386.7 F/g(1 A/g) | 96.8%(20000 cycles) | [ |
MoSe2/MoS2 | 0.5 mol/L H2SO4 | 1229.6 F/g(1 A/g) | 92.8%(2000 cycles) | [ |
MoS2/CNT | 1 mol/L Na2SO4 | 337 mF/cm2 | 97.6%(2500 cycles) | [ |
MoSe2/Ni foam | 6 mol/L KOH | 1114.1 F/g(1 A/g) | 104.7%(1500 cycles) | [ |
Flake MoSe2 | 1 mol/L Na2SO4 | 1467.8 F/g(4 mA/cm2) | 80%(1000 cycles) | [ |
MoSe2/rGO | 6 mol/L KOH | 1422 F/g(1 A/g) | 100.7%(1500 cycles) | [ |
MoSe2/Acetylene black | 6 mol/L KOH | 2020 F/g(1 A/g) | 107.5%(1500 cycles) | [ |
1T’?MoSe2@rGO | — | 1791 F/g(1 A/g) | 98.6%(2000 cycles) | [ |
Fig.8 One?body array of core/shell nanowire supercapacitor and electrochemical performance[102](A) Schematic illustration for one-body array of core/shell nanowire supercapacitor; (B) TEM image of cross-section h-WO3/WS2 core/shell nanowire; (C) optical image of as-prepared core/shell nanowires on a W foil under mechanical bending(left), corresponding SEM image(right) shows high-density; (D) demonstration of powering a LED.Copyright 2016, American Chemical Society.
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
WS2/rGO | 1 mol/L Na2SO4 | 350 F/g(0.5 A/g) | 1000 cycles | [ |
h?WO3/WS2 | 0.1 mol/L Na2SO4 | 47.5 mF/cm2(0.5 mA/cm2) | 30000 cycles | [ |
WS2/Co3S4 | 1 mol/L H2SO4 | 412.7 F/g(1 A/g) | 94.3%(2000 cycles) | [ |
WS2/PEDOT | 1 mol/L Na2SO4 | 70.64 F/g(0.2 A/g) | 90.74%(5000 cycles) | [ |
WS2/rGO | 1 mol/L H2SO4 | 383.6 F/g(0.5 A/g) | 102.5%(10000 cycles) | [ |
WS2 Quantum dots | PVA?H3PO4 | 28 mF/cm2(0.1 mA/cm2) | 80%(10000 cycles) | [ |
WS2?MWCNTs/PANI | 1 mol/L H2SO4 | ca. 760.1 F/g(1 A/g) | ca. 80.2%(2000 cycles) | [ |
WS2@NiCo2O4 | 3 mol/L KOH | 2449.9 mF/cm2(1 mA/cm) | [ | |
WSe2 | 1 mol/L H2SO4 | 43.6 F/g(0.2 A/g) | 99%(20000 cycles) | [ |
WTe2 | PVA?H3PO4 | 221 F/g(1 A/g) | 91%(5500 cycles) | [ |
WSe2/rGO | 3 mol/L KOH | 389 F/g(1 A/g) | 98.7%(3000 cycles) | [ |
Table 3 Tungsten-based TMDs supercapacitor performance comparison
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
WS2/rGO | 1 mol/L Na2SO4 | 350 F/g(0.5 A/g) | 1000 cycles | [ |
h?WO3/WS2 | 0.1 mol/L Na2SO4 | 47.5 mF/cm2(0.5 mA/cm2) | 30000 cycles | [ |
WS2/Co3S4 | 1 mol/L H2SO4 | 412.7 F/g(1 A/g) | 94.3%(2000 cycles) | [ |
WS2/PEDOT | 1 mol/L Na2SO4 | 70.64 F/g(0.2 A/g) | 90.74%(5000 cycles) | [ |
WS2/rGO | 1 mol/L H2SO4 | 383.6 F/g(0.5 A/g) | 102.5%(10000 cycles) | [ |
WS2 Quantum dots | PVA?H3PO4 | 28 mF/cm2(0.1 mA/cm2) | 80%(10000 cycles) | [ |
WS2?MWCNTs/PANI | 1 mol/L H2SO4 | ca. 760.1 F/g(1 A/g) | ca. 80.2%(2000 cycles) | [ |
WS2@NiCo2O4 | 3 mol/L KOH | 2449.9 mF/cm2(1 mA/cm) | [ | |
WSe2 | 1 mol/L H2SO4 | 43.6 F/g(0.2 A/g) | 99%(20000 cycles) | [ |
WTe2 | PVA?H3PO4 | 221 F/g(1 A/g) | 91%(5500 cycles) | [ |
WSe2/rGO | 3 mol/L KOH | 389 F/g(1 A/g) | 98.7%(3000 cycles) | [ |
Fig.9 VS2 ultra?thin nanosheets for high two?dimensional conductivity of planar supercapacitors[112](A) VS2 thin films of different thicknesses are transferred to quartz substrate; (B) temperature dependence of planar resistivity of VS2 thin film; (C) planar ion migration pathways for the in-plane supercapacitor and schematic illustration of the in-plane configuration of the as-fabricated supercapacitor. Copyright 2011, American Chemical Society.
Fig.10 Synthesis and electrochemical performance of defect?rich VS2 nanoplates[115](A) Schematic illustration of the formation process of rich-defect VS2 nanoplate; (B) comparison of the energy density vs. power density curves of the full cell and other works; (C) two asymmetric supercapacitors were connected in series to light an OUC light-emitting diode(LED) panel. Copyright 2018, Royal Society of Chemistry.
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
VS2 | PVA?BMIMBF4 | 4760 μF/cm2 | >90%(1000 cycles) | [ |
VS2/MWCNTs | 2 mol/L KCl | 830 F/g | 95.9%(10000 cycles) | [ |
VS2/C | PVA/H2SO4 | 86.4 F/cm3(0.1 mA/cm2) | 97.7%(10000 cycles) | [ |
VS2 | 1 mol/L KOH | 2200 F/g(1 A/g) | [ | |
NiCo2S4@VS2 | 3 mol/L KOH | 1023.4 C/g(0.45 A/g) | 96%(2000 cycles) | [ |
VS2/ZnO | 1 mol/L KOH | 2695.7 F/g(1 A/g) | 92.7%(5000 cycles) | [ |
VSe2/rGO | 680 F/g(1 A/g) | ca. 81%(10000 cycles) | [ | |
VSe2/rGO | 2 mol/L KOH | 1129 F/g(1 A/g) | 89.76%(2000 cycles) | [ |
Table 4 Vanadium-based TMDs supercapacitor performance comparison
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
VS2 | PVA?BMIMBF4 | 4760 μF/cm2 | >90%(1000 cycles) | [ |
VS2/MWCNTs | 2 mol/L KCl | 830 F/g | 95.9%(10000 cycles) | [ |
VS2/C | PVA/H2SO4 | 86.4 F/cm3(0.1 mA/cm2) | 97.7%(10000 cycles) | [ |
VS2 | 1 mol/L KOH | 2200 F/g(1 A/g) | [ | |
NiCo2S4@VS2 | 3 mol/L KOH | 1023.4 C/g(0.45 A/g) | 96%(2000 cycles) | [ |
VS2/ZnO | 1 mol/L KOH | 2695.7 F/g(1 A/g) | 92.7%(5000 cycles) | [ |
VSe2/rGO | 680 F/g(1 A/g) | ca. 81%(10000 cycles) | [ | |
VSe2/rGO | 2 mol/L KOH | 1129 F/g(1 A/g) | 89.76%(2000 cycles) | [ |
Fig.11 Preparation and electrochemical performance of NiSe2 PNSvac[123](A) Schematic procedure for the preparation of NiSe2 PNSvac; (B) CV curves of NiSe2 PNSvac, NiSe2 NS, and NiSe2 particle at a scan rate of 10 mV/s; (C) the specific capacitance of NiSe2 PNSvac, NiSe2 NS, and NiSe2 particle at different current density. Copyright 2018, American Chemical Society.
Fig.12 Preparation and electrochemical performance of acid?assisted exfoliation of TaS2 monolayer[127](A) By acid-assisted exfoliation, LiTaS2 single crystal swelled with TaS2 layer etched, achieving conductive TaS2 monolayers with large lateral size and sub-nanopore structure; (B) HAADF image of the corresponding TaS2 monolayer; (C) pore size distribution of TaS2 film by density functional theory(DFT) mode; (D) volumetric capacitance of MSP-TaS2 and SI-TaS2 based MSC as a function of scan rates; (E) cycling stability of MSP-TaS2 based MSC measured at 2 A/g. Inset: (D) the corresponding gravimetric capacitance as a function of scan rates; (E) comparison of GCD curves between the 1st cycle and the 4000th cycle for MSP-TaS2 based MSC. Copyright 2017, American Chemical Society.
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
NiSe2 | 4 mol/L KOH | 1044 F/g(3 A/g) | 67%(2000 cycles) | [ |
NiSe2/CFC | 3 mol/L KOH | 1058 F/g(2 A/g) | [ | |
NiSe2 PNSvac | 1 mol/L KOH | 466 F/g(3 A/g) | 81.3%(1000 cycles) | [ |
Ni3Se2 | 3 mol/L KOH | 635 μA·h/cm2(3 mA/cm2) | [ | |
TiS2/VACNT | 21 mol/L LiTFSI | 195 F/g | ca. 95%(10000 cycles) | [ |
TaS2/PPy | 1 mol/L H2SO4 | 835 F/cm2 | 98.7%(10000 cycles) | [ |
CoSe2 | 3 mol/L KOH | 544.6 F/g(1 mA/cm2) | 93.3%(5000 cycles) | [ |
CoSe2 | 3 mol/L KOH | 759.5 F/g(1 mA/cm2) | 94.5%(5000 cycles) | [ |
NiGa2S4 | 6 mol/L KOH | 2225 F/g(2 A/g) | 78.9%(6000 cycles) | [ |
Table 5 Performance comparison of other TMDs supercapacitors
Electrode material | Electrolyte | Capacitance | Cycle performance | Ref. |
---|---|---|---|---|
NiSe2 | 4 mol/L KOH | 1044 F/g(3 A/g) | 67%(2000 cycles) | [ |
NiSe2/CFC | 3 mol/L KOH | 1058 F/g(2 A/g) | [ | |
NiSe2 PNSvac | 1 mol/L KOH | 466 F/g(3 A/g) | 81.3%(1000 cycles) | [ |
Ni3Se2 | 3 mol/L KOH | 635 μA·h/cm2(3 mA/cm2) | [ | |
TiS2/VACNT | 21 mol/L LiTFSI | 195 F/g | ca. 95%(10000 cycles) | [ |
TaS2/PPy | 1 mol/L H2SO4 | 835 F/cm2 | 98.7%(10000 cycles) | [ |
CoSe2 | 3 mol/L KOH | 544.6 F/g(1 mA/cm2) | 93.3%(5000 cycles) | [ |
CoSe2 | 3 mol/L KOH | 759.5 F/g(1 mA/cm2) | 94.5%(5000 cycles) | [ |
NiGa2S4 | 6 mol/L KOH | 2225 F/g(2 A/g) | 78.9%(6000 cycles) | [ |
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