Research progress on metal and covalent organic framework-based materials for high-performance supercapacitors
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摘要: 金属有机骨架(MOFs)和共价有机骨架(COFs)是一系列结晶多孔材料。 由于其高度有序的结构、高的表面积、可调的孔径和拓扑结构、富含氧化还原活性位点的连续骨架,MOFs和COFs及其衍生物在储能领域引起了广泛关注。 为了制造高性能超级电容器电极,MOFs 和 COFs 及其衍生物具有结构稳定性好、氧化还原活性位点丰富和电子导电性高等特征。 本文回顾了近年来 MOFs 和 COFs材料、MOFs 和 COFs 与导电材料(导电聚合物、石墨烯、碳纳米管)的复合材料、MOFs 和 COFs 衍生炭材料的设计策略,以及所得材料的物化特性、电容性能的研究进展,并介绍了结构和性能之间的关系。 最后,提出了基于 MOFs 和 COFs电极材料的挑战和前景。Abstract: Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are both a series of crystalline porous materials. MOFs, COFs and their derivatives have attracted much attention in energy storage devices due to their highly ordered structures, large surface areas, tunable pore sizes and topologies, and well-defined redox-active porous skeletons. They must also have structural stability, an abundance of redox-active sites and high electronic conductivity for use in high-performance supercapacitor electrodes. We review the recent research progress on the design of MOFs and COFs, and their hybrids with conductive materials (e.g. conductive polymer, graphene and carbon nanotubes), and MOF- and COF-derived carbon materials. Their chemical and physical properties, capacitive performance and structure-property relationships are discussed. Finally, the challenges and prospects of MOF- and COF-based electrode materials are presented.
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Key words:
- Metal-organic frameworks /
- Covalent organic frameworks /
- Hybrid /
- Derived carbon /
- Supercapacitors
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Figure 4. (a) Schematic illustration of BTCC preparation and the cycling stability of the two devices for 10000 GCD cycles at a current density of 20 A·g−1, (insert: an LED indicator in the assembled SC based on 1 mol·L−1 Na2SO4)[61]. (b) Schematic of the preparation process of UAC@NF and cycling stability over 10000 cycles (4 mA·cm−2), (inset) optical image showed three pieces of the ASC device connected in series to power a LED[62]. (c) Schematic for the synthesis process of HA-CoFe-ZIF and NCS and cycling stability, coulombic efficiency of the NCS-650//AC asymmetric SC[63]. Reprinted with permission.
Figure 5. (a) Layered structure of TpOMe-DAQ. (b) Redox behavior of TpOMe-DAQ through reversible quinine to hydroquinone transformation. (c) Cross section SEM analysis of TpOMe-DAQ thin sheet. (d) Cyclic voltammetry of the as-synthesized sheets[67]. (e) Synthesis of β-ketoenamine-linked 2D COFs[68]. Reprinted with permission.
Figure 6. (a) Synthesis scheme of TTF-COF1[73]. (b) Synthesis procedure and chemical structure of PG-BBT[74]. Electrochemical measurement of PG-BBT in a three-electrode system: (c) CV profiles at various scan rates (5–30 mV·s−1). (d) GCD curves at various current densities (1–10 A·g−1). (e) Capacitance at various current densities (1–10 A·g−1). Reprinted with permission.
Figure 7. (a) Synthesis and structures of olefin-linked 2D conjugated polymer framework by Knoevenagel reaction[76]. (b) Synthesis and structure of g-C34N6-COF[77]. (c) Synthetic routes to g-C30N6-COF and g-C48N6-COF[78]. (d) SEM graph of g-C30N6-COF. (e) CV curves of g-C30N6-COF-MSC. (f) The specific areal and volumetric capacitances (CA and CV) of g-C30N6-COF-MSC and g-C48N6-COF-MSC. Reprinted with permission.
Figure 8. (a) Synthesis procedure of a DAAQ-COF/GA composite[85]. Electrochemical performances of the DAAQ-COF/GA//GA asymmetric SC (ASC). (b) CV curves of the ASC with different scan rates. (c) GCD curves of the ASC at various current densities. (d) Cycling stability test at 5 A·g-1 for 20 000 cycles (the inset shows the digital photograph of LEDs powered by the DAAQ-COFs/GA//GA ASC). (e) Schematic illustration of template synthesis of [C60]X-COFs[88]. Reprinted with permission.
Figure 9. (a) Synthesis procedure of ACOF1. (b) GCD curves at various current densities of the carbonized ACOF1[115]. (c) The synthesis procedure of COF-TP, GCD curves of (d) COF-TP and (e) COF-TP-C at different current densities within the potential windows of 0-0.40 V[117]. (f) Schematic illustration of the formation of hierarchically porous B-doped carbons from COF-5 using the molten-salt approach. (g) Cyclic voltammograms of BC-MS-700-14 at sweep rates from 10 to 400 mV·s−1. (h) Galvanostatic charge–discharge curves at different current densities[118]. Reprinted with permission.
Figure 10. (a) Synthetic scheme and PXRD pattern of Ni-COF. (b) Energy storage and conversion diagram of Ni-COF. (c) GCD curves of Ni-COF (1-10 A·g−1). (d) Comparison of GCD curves of Ni-COF and Ni0-COF at 1 A·g−1. (e) Comparison of Nyquist plots of Ni-COF and Ni0-COF[121]. Reprinted with permission.
Table 1. Selected properties of MOFs-based materials for SCs.
Three-electrode system Device Ref. Electrode materials Electrolyte Cap
(F·g−1)Current density
(A·g−1)Electrode materials Electrolyte Capacity
(F·g−1)Current density
(A·g−1)Energy density
(W h·kg−1)Power density
(W·kg−1)Ni-MOF 3 mol·L−1 KOH 988 1.4 -//AC H2SO4-PVA gel 230 mF·cm−2 1 A·cm−2 4.18 mW h·cm−3 231.2 mW·cm−3 [31] Co-LMOF 1 mol·L−1 KOH 2474 1 [33] Ni/Co-MOF 2 mol·L−1 KOH 1230.3 1 -//AC 2 mol·L−1 KOH 328 1 116 0.795 [37] Mn-MOF 2 mol·L−1 KOH 567.5 mA h·g−1 1 -//rGO 2 mol·L−1 KOH 211.4 5 66 441 [41] Ni3(HITP)2 symmetric 1 MTEABF4/ACN 111 0.05 [43] Cu–CAT NWAs 3 mol·L−1 KCl 202 0.5 symmetric PVA/KCl gel 120 0.5 ~2.6 ~200 [44] NHMO-5 3 mol·L−1 KOH 368.2 1 -//AC 3 mol·L−1 KOH 178.9 1 600 35.8 [45] 2D c-MOFs -//EC PVA/LiCl gel 18.9 mF·cm−1 0.04 mA·cm−2 1.7 mA h·cm−2 168 mW·cm−2 [46] Cu3(HHTP)2 3 mol·L−1 KCl 1700 µF·cm−2 30 µA·cm−2 symmetric PVA/KCl gel 939.2 µF·cm−2 7 µA·cm−2 0.047 µW h·cm−2 2.1 µW·cm−2 [47] nMOF-867 symmetric 1mol·L−1 (C2H5)4NBF4 0.644 F·cm−3 6.04×10−4 W h·cm−3 1.097 W·cm−3 [49] CoMG5 6 mol·L−1 KOH 549.96 10 mV·s−1 -//AC 6 mol·L−1 KOH 50.2 20 mV·s−1 8.1 850 [50] NCMOF/EGP 2 mol·L−1 KOH 2.41 F·cm−2 0.5 mA·cm−2 -//AC 0.36 F·cm−2 1 A·cm−2 0.11 mW h·cm−2 0.75 mW·cm−2 [51] Ni-MOF/CNTs 6 mol·L−1 KOH 1765 0.5 -//rGO/g-C3N4 6 mol·L−1 KOH 103 0.5 36.6 480 [52] Ni-MOF@CNT -//AC PVA-KOH gel 898 mF·cm−2 1 mA·cm−2 0.3396 mW h·cm−2 [53] PEDOT-GO/U-C symmetric H3PO4-PVA gel 30 mF·cm−2 5 mV·s−1 0.0022 mW h·cm−2 0.2 mW·cm−2 [54] PPy@NiCo-CAT 2 mol·L−1 KOH 572.2 1 -//AC 2 mol·L−1 KOH 65 0.5 22.22 400 [55] PANI-ZIF-67-CC 3 mol·L−1 KCl 2146 mF·cm−2 10 mV·s−1 symmetric H2SO4-PVA gel 35 mF·cm−2 0.05 mA·cm−2 0.833 W·cm−3 0.0161 mW h·cm−3 [56] p-PPy/Cu-CAT 3 mol·L−1 KCl 480 mF·cm−2 0.5 mA·cm−2 symmetric PVA/LiCl gel 233 mF·cm−2 0.5 mA·cm−2 12 μW h·cm−2 1.5 mW·cm−2 [57] rGO-HKUST-1 0.5 mol·L−1 Na2SO4 377 100 mV·s−1 symmetric NaNO3-PVA gel 193 42 3100 [58] C-Co@MOF 0.6 -//N-CNT KOH-PVA gel 118.3 3 37 2250.2 [59] BTCC 6 mol·L−1 KOH 285 1 symmetric 6 mol·L−1 KOH 101.7 1 13.7 650 [61] symmetric 1 mol·L−1 Na2SO4 99.8 1 2.4 450 UAC@NF 3 mol·L−1 KOH 524.6 mF·cm−2 1 mA·cm−2 -//GF500 3 mol·L−1 KOH 263.6 mF·cm−2 0.3 mA·cm−2 0.036 mWh·cm−3 0.984 mW·cm−3 [62] NCS-650 6 mol·L−1 KOH 324 1 -//AC 6 mol·L−1 KOH 93 1 10.3 331 [63] CMP-25 6 mol·L−1 KOH 385 0.1 symmetric 6 mol·L−1 KOH 10.51 5454 [64] NSPC 6 mol·L−1 KOH 386.3 1 6 mol·L−1 KOH 186.9 1 50.9 1600 [65] Table 2. Selected properties of COFs-based materials for SCs.
Three-electrode system Device Ref. Electrode materials Electrolyte Cap
(F·g−1)Current density
(A·g−1)Electrode materials Electrolyte Capacity
(F·g−1)Current
density
(A·g−1)Energy
density
(W h·kg−1)power density
(W·kg−1)TFP-NDA-COF 1 mol·L−1 H2SO4 348 0.5 [66] TpOMe-DAQ 3 mol·L−1 H2SO4 1600 mF·cm−2 3.3 A·cm−2 Symmetric H2SO4/PVA gel 84 mF·cm−2 0.25 mA·cm−2 ~2.9 μW h·cm−2 ~61.8 μW·cm−2 [67] Dq1Da1Tp 1 mol·L−1 H2SO4 111 1.56 mA·cm−2 Symmetric H2SO4-PVA gel 8.5 mF·cm−2 0.39mA·cm−2 0.30 μW h·cm−2 960 μW·cm−2 [68] PDC-MA-COF 6 mol·L−1 KOH 335 1 -//AC 6 mol·L−1 KOH 94 1 29.2 750 [69] TPA-COFs 1 mol·L−1 H2SO4 263.1 0.1 [70] TFP-TPA COF 1mol·L−1 KOH 291.1 2 [71] TTF-COF1 3 mol·L−1 KOH 752 1 -//AC 3 mol·L−1 KOH 183 1 57 858 [73] PG-BBT 3 mol·L−1 KOH 724 1 -//AC 3 mol·L−1 KOH 220 1 69 1010 [74] 2DPPV-800 6 mol·L−1 KOH 334 0.5 [76] g-C34N6-COF/CNT LiCl/PVA gel 15.2 2 mV·s−1 7.3 mW h·cm−3 0.05 W·cm−3 [77] g-C30N6-COF EMIMBF4/PVDF-HFP 44.3 mF·cm−2 5mV·s−1 38.5 mW h·cm−3 0.3 W·cm−3 [78] P1 1 mol·L−1 H2SO4 805 0.5 [79] PEDOT@AQ-COF 1 mol·L−1 H2SO4 1663 1 1 mol·L−1 H2SO4 1663 1 [80] TpPa-COF@PANI 1 mol·L−1 H2SO4 95 0.2 [81] aza-MOFs@COFs Symmetric (C2H5)4NBF4 20.35 mF·cm−2 0.2 A·cm−2 [82] BIBDZ 1mol·L−1 H3PO4 88.4 0.5 [84] DAAQ-COFs/GA 1 mol·L−1 H2SO4 378 1 -//GA 1 mol·L−1 H2SO4 112 1 30.5 700 [85] COFs/NH2–rGO 1 mol·L−1 Na2SO4 533 0.2 [86] [C60]0.05-COF 1 mol·L−1 Na2SO4 63.1 0.7 -//rGO 1 mol·L−1 Na2SO4 47.6 4 21.4 900 [88] CNT/NKCOF-2 2 mol·L−1 H2SO4 440 0.5 -//AC H2SO4-PVA gel 263 1 71 42 [95] TCNQ-CTF-800 1 mol·L−1 KOH 383 0.2 Symmetric EMIM BF4 100 0.1 42.8 8750 [102] TPI-P-700 1 mol·L−1 H2SO4 423 2 Symmetric 1 mol·L−1 H2SO4 304 0.5 10.5 5000 [103] PTF-700 Symmetric EMIMBF4 151.3 0.1 62.7 8750 [104] p-CTF-800 1 mol·L−1 H2SO4 406 0.2 Symmetric 1 mol·L−1 H2SO4 245.7 0.2 6.9 50 [105] Symmetric EMIMBF4 181 0.2 77 175 FCTF 1 mol·L−1 H2SO4 379 1 -//AC 1 mol·L−1 H2SO4 148 1 46.3 975 [106] CTF-800 1 mol·L−1 H2SO4 628 0.5 Symmetric 1 mol·L−1 H2SO4 448 0.5 15.5 125 [108] EMIMBF4 222 0.5 70 375 1 mol·L−1 LiPF6 251 0.5 78 375 FUM-700 6 mol·L−1 KOH 400 1 Symmetric 6 mol·L−1 KOH 275 1 18 325 [109] PDC-MA-COF 6 mol·L−1 KOH 335 1 -//AC 6 mol·L−1 KOH 94 1 29.2 750 [110] TPT-DAHQ COF 1 mol·L−1 KOH 256 0.5 [111] TDFP-1 0.1 mol·L−1 H2SO4 418 0.5 [112] THPC 6 mol·L−1 KOH 235 1 Symmetric EMIMBF4 103 0.5 50.45 350 [113] Symmetric 6 mol·L−1 KOH 183 0.2 Symmetric 1 mol·L−1 Na2SO4 81 10 LNU-18-800 6 mol·L−1 KOH 269 0.5 [114] ACOF1 6 mol·L−1 KOH 234 1 [115] N-MCS-200 6 mol·L−1 KOH 292 1 Symmetric 6 mol·L−1 KOH 251 1 8.75 500 [116] BC-MS-700-14 1 mol·L−1 H2SO4 160 10 mV·s−1 [118] PCCOF-5 Symmetric TEABF4 15.3 mF·cm−2 0.04 [119] B-C-N-1000 6 mol·L−1 KOH 230 5 [120] Ni-COF 3 mol·L−1 KOH 1478 0.5 -//AC 3 mol·L−1 KOH 417 1 130 839 [121] (N)G2 6 mol·L−1 KOH 460 1 Symmetric 6 mol·L−1 KOH 175 0.2 6.1 50 [122] -
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