All-Covalent Organic Framework Nanofilms Assembled Lithium-Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics

doi:10.1007/s40820-024-01343-2

Abstract

Abstract:

Free-standing covalent organic framework (COFs) nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li⁺ in lithium-ion batteries, while simultaneously exposing affluent active sites in supercapacitors. The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors (LICs). Herein, for the first time, custom-made COF_BTMB-TP and COF_TAPB-BPY nanofilms are synthesized as the anode and cathode, respectively, for an all-COF nanofilm-structured LIC. The COF_BTMB-TP nanofilm with strong electronegative-CF₃ groups enables tuning the partial electron cloud density for Li⁺ migration to ensure the rapid anode kinetic process. The thickness-regulated cathodic COF_TAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity. Due to the aligned 1D channel, 2D aromatic skeleton and accessible active sites of COF nanofilms, the whole COF_TAPB-BPY//COF_BTMB-TP LIC demonstrates a high energy density of 318 mWh cm⁻³ at a high-power density of 6 W cm⁻³, excellent rate capability, good cycle stability with the capacity retention rate of 77% after 5000-cycle. The COF_TAPB-BPY//COF_BTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors. After being comprehensively explored via ex situ XPS, ⁷Li solid-state NMR analyses, and DFT calculation, it is found that the COF_BTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C-F bonds during lithium storage. COF_BTMB-TP exhibits a strong interaction with Li⁺ due to the C-F, C=O, and C-N bonds, facilitating Li⁺ desolation and absorption from the electrolyte. This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

Key words: Covalent organic frameworks, Lithium-ion capacitor, Charge storage kinetic

Xiaoyang Xu, Jia Zhang, Zihao Zhang, Guandan Lu, Wei Cao, Ning Wang, Yunmeng Xia, Qingliang Feng, Shanlin Qiao. All-Covalent Organic Framework Nanofilms Assembled Lithium-Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics[J]. Nano-Micro Letters, 2024, 16(1): 116-.

Xiaoyang Xu, Jia Zhang, Zihao Zhang, Guandan Lu, Wei Cao, Ning Wang, Yunmeng Xia, Qingliang Feng, Shanlin Qiao. [J]. Nano-Micro Letters, 2024, 16(1): 116-.

/ / Recommend / Download Citations

URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01343-2

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/116

Figures/Tables 5

Scheme 1 Schematic synthesis of COF_TAPB-BPY and COF_BTMB-TP nanofilms (a); illustration of assembling COF_TAPB-BPY//COF_BTMB-TP nanofilm LIC (b)

Fig. 1 OM (a‒b), Raman spectra (inset)), SEM (c‒d), TEM (e‒f), AFM (g‒h), SECM (i‒l) images of COF_TAPB-BPY and COF_BTMB-TP nanofilms

Fig. 2 CV curves at different scan rates (a), GCD curves at different current densities (b), rate capacity (c), cycling stability properties after 1000 cycles (d) and ex situ XPS spectra of C-F bonds in LiClO₄ (1 M, in EC:PC = 1:1 Vol%) alternative electrolyte (e) for COF_BTMB-TP electrode; solid-state ⁷Li NMR spectra of LiPF₆ with and without COF_BTMB-TP addition (f); DFT simulated Li⁺ adsorption energy about COF_BTMB-TP and electrolyte components (g), calculated electrostatic potential distribution of COF_BTMB-TP (inset, g); schematic descriptions of Li.⁺ migration process from electrolyte components to COF_BTMB-TP (h)

Fig. 3 Capacitive contribution marked CV curve at 1 mV s⁻¹ (a), surface capacitance and diffusion-controlled proportion (b), dynamic Nyquist plots at various discharge potentials (c), plots of Z’ vs. ω^−1/2 (d) of COF_BTMB-TP nanofilms; Li⁺ diffusion coefficient of COF_BTMB-TP nanofilms and powder (e); effect of the concentration of TAPB monomer on the thickness of COF_TAPB-BPY nanofilm and energy density of COF_TAPB-BPY//COF_BTMB-TP nanofilm LIC device (f)

Fig. 4 CV (a) and GCD (b) curves, C_A and C_V (c), Ragone (d) and Nyquist (e) plots, cycle stability and coulombic efficiency (f), self-discharge performance (g) of the COF_TAPB-BPY//COF_BTMB-TP nanofilm LIC; energy barrier of Li⁺ diffusion control step in anode COF_BTMB-TP structure (h); performance evaluation of COF_TAPB-BPY//COF_BTMB-TP nanofilm LICs (i)

References 44

1.	A. Jagadale, X. Zhou, R. Xiong, D.P. Dubal, J. Xu et al., Lithium ion capacitors (LICs): development of the materials. Energy Storage Mater. 19, 314-329 (2019). https://doi.org/10.1016/j.ensm.2019.02.031
2.	H. Gu, Y.-E. Zhu, J. Yang, J. Wei, Z. Zhou, Nanomaterials and technologies for lithium-ion hybrid supercapacitors. ChemNanoMat 2, 578-587 (2016). https://doi.org/10.1002/cnma.201600068
3.	L. Gao, D. Huang, Y. Shen, M. Wang, Rutile-TiO₂ decorated Li₄Ti₅O₁₂ nanosheet arrays with 3D interconnected architecture as anodes for high performance hybrid supercapacitors. J. Mater. Chem. A 3, 23570-23576 (2015). https://doi.org/10.1039/C5TA07666H
4.	B. Li, J. Zheng, H. Zhang, L. Jin, D. Yang et al., Electrode materials, electrolytes, and challenges in nonaqueous lithium-ion capacitors. Adv. Mater. 30, 1705670 (2018). https://doi.org/10.1002/adma.201705670
5.	H. Xu, X. Hu, Y. Sun, W. Luo, C. Chen et al., Highly porous Li₄ Ti₅O₁₂/C nanofibers for ultrafast electrochemical energy storage. Nano Energy 10, 163-171 (2014). https://doi.org/10.1016/j.nanoen.2014.09.003
6.	S. Weng, G. Yang, S. Zhang, X. Liu, X. Zhang et al., Kinetic limits of graphite anode for fast-charging lithium-ion batteries. Nano-Micro Lett. 15, 215 (2023). https://doi.org/10.1007/s40820-023-01183-6
7.	H. Kim, M.-Y. Cho, M.-H. Kim, K.-Y. Park, H. Gwon et al., A novel high-energy hybrid supercapacitor with an anatase TiO₂-reduced graphene oxide anode and an activated carbon cathode. Adv. Energy Mater. 3, 1500-1506 (2013). https://doi.org/10.1002/aenm.201300467
8.	W. Zhu, S.A. El-Khodary, S. Li, B. Zou, R. Kang et al., Roselle-like Zn₂Ti₃O₈/rGO nanocomposite as anode for lithium ion capacitor. Chem. Eng. J. 385, 123881 (2020). https://doi.org/10.1016/j.cej.2019.123881
9.	S. Li, J. Chen, M. Cui, G. Cai, J. Wang et al., A high-performance lithium-ion capacitor based on 2D nanosheet materials. Small 13, 1602893 2017). https://doi.org/10.1002/smll.201602893
10.	Z. Xiao, J. Han, H. He, X. Zhang, J. Xiao et al., A template oriented one-dimensional Schiff-base polymer: towards flexible nitrogen-enriched carbonaceous electrodes with ultrahigh electrochemical capacity. Nanoscale 13, 19210-19217 (2021). https://doi.org/10.1039/D1NR05618B
11.	G. Yan, X. Sun, Y. Zhang, H. Li, H. Huang et al., Metal-free 2D/2D van der Waals heterojunction based on covalent organic frameworks for highly efficient solar energy catalysis. Nano-Micro Lett. 15, 132 (2023). https://doi.org/10.1007/s40820-023-01100-x
12.	M.S. Lohse, T. Bein, Covalent organic frameworks: structures, synthesis, and applications. Adv. Funct. Mater. 28, 1705553 (2018). https://doi.org/10.1002/adfm.201705553
13.	S. Wang, Q. Wang, P. Shao, Y. Han, X. Gao et al., Exfoliation of covalent organic frameworks into few-layer redox-active nanosheets as cathode materials for lithium-ion batteries. J. Am. Chem. Soc. 139, 4258-4261 (2017). https://doi.org/10.1021/jacs.7b02648
14.	S. Jin, O. Allam, S.S. Jang, S.W. Lee, Covalent organic frameworks: design and applications in electrochemical energy storage devices. InfoMat 4, e12277 (2022). https://doi.org/10.1002/inf2.12277
15.	H. Yang, S. Zhang, L. Han, Z. Zhang, Z. Xue et al., High conductive two-dimensional covalent organic framework for lithium storage with large capacity. ACS Appl. Mater. Interfaces 8, 5366-5375 (2016). https://doi.org/10.1021/acsami.5b12370
16.	W. Yan, F. Yu, Y. Jiang, J. Su, S.-W. Ke et al., Self-assembly construction of carbon nanotube network-threaded tetrathiafulvalene-bridging covalent organic framework composite anodes for high-performance hybrid lithium-ion capacitors. Small Struct. 3, 2200126 (2022). https://doi.org/10.1002/sstr.202200126
17.	Q. Geng, H. Wang, J. Wang, J. Hong, W. Sun et al., Boosting the capacity of aqueous Li-ion capacitors via pinpoint surgery in nanocoral-like covalent organic frameworks. Small Methods 6, e2200314 (2022). https://doi.org/10.1002/smtd.202200314
18.	Y. Wang, N. Chen, B. Zhou, X. Zhou, B. Pu et al., NH₃-induced in situ etching strategy derived 3D-interconnected porous MXene/carbon dots films for high performance flexible supercapacitors. Nano-Micro Lett. 15, 231 (2023). https://doi.org/10.1007/s40820-023-01204-4
19.	X. Xu, R. Xiong, Z. Zhang, X. Zhang, C. Gu et al., Space-partitioning and metal coordination in free-standing covalent organic framework nano-films: over 230 mWh/cm³ energy density for flexible in-plane micro-supercapacitors. Chem. Eng. J. 447, 137447 (2022). https://doi.org/10.1016/j.cej.2022.137447
20.	H. Zong, A. Zhang, J. Dong, Y. He, H. Fu et al., Flexible asymmetric supercapacitor based on open-hollow nickel-MOFs/reduced graphene oxide aerogel electrodes. Chem. Eng. J. 475, 146088 (2023). https://doi.org/10.1016/j.cej.2023.146088
21.	H. Guo, A. Zhang, H. Fu, H. Zong, F. Jin et al., In situ generation of CeCoS_x bimetallic sulfide derived from “egg-box” seaweed biomass on S/N Co-doped graphene aerogels for flexible all solid-state supercapacitors. Chem. Eng. J. 453, 139633 (2023). https://doi.org/10.1016/j.cej.2022.139633
22.	Q. Zhang, S. Liu, J. Huang, H. Fu, Q. Fan et al., In situ selective selenization of ZIF-derived CoSe₂ nanoparticles on NiMn-layered double hydroxide@CuBr₂ heterostructures for high performance supercapacitors. J. Colloid Interface Sci. 655, 273-285 (2024). https://doi.org/10.1016/j.jcis.2023.11.008
23.	A. Zhang, Q. Zhang, H. Fu, H. Zong, H. Guo, Metal-organic frameworks and their derivatives-based nanostructure with different dimensionalities for supercapacitors. Small 19, e2303911 (2023). https://doi.org/10.1002/smll.202303911
24.	H. Sahabudeen, H. Qi, M. Ballabio, M. Položij, S. Olthof et al., Highly crystalline and semiconducting imine-based two-dimensional polymers enabled by interfacial synthesis. Angew. Chem. Int. Ed. 59, 6028-6036 (2020). https://doi.org/10.1002/anie.201915217
25.	K. Liu, H. Qi, R. Dong, R. Shivhare, M. Addicoat et al., On-water surface synthesis of crystalline, few-layer two-dimensional polymers assisted by surfactant monolayers. Nat. Chem. 11, 994-1000 (2019). https://doi.org/10.1038/s41557-019-0327-5
26.	S. Kim, H. Lim, J. Lee, H.C. Choi, Synthesis of a scalable two-dimensional covalent organic framework by the photon-assisted imine condensation reaction on the water surface. Langmuir 34, 8731-8738 (2018). https://doi.org/10.1021/acs.langmuir.8b00951
27.	V. Augustyn, J. Come, M.A. Lowe, J.W. Kim, P.L. Taberna et al., High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 12, 518-522 (2013). https://doi.org/10.1038/nmat3601
28.	C. Wang, F. Liu, J. Chen, Z. Yuan, C. Liu et al., A graphene-covalent organic framework hybrid for high-performance supercapacitors. Energy Storage Mater. 32, 448-457 (2020). https://doi.org/10.1016/j.ensm.2020.07.001
29.	K. Jiang, I.A. Baburin, P. Han, C. Yang, X. Fu et al., Interfacial approach toward benzene-bridged polypyrrole film-based micro-supercapacitors with ultrahigh volumetric power density. Adv. Funct. Mater. 30, 1908243 (2020). https://doi.org/10.1002/adfm.201908243
30.	Y. Yang, X. Zhao, H.-E. Wang, M. Li, C. Hao et al., Phosphorized SnO₂/graphene heterostructures for highly reversible lithium-ion storage with enhanced pseudocapacitance. J. Mater. Chem. A 6, 3479-3487 (2018). https://doi.org/10.1039/C7TA10435A
31.	S. Kandambeth, A. Mallick, B. Lukose, M.V. Mane, T. Heine et al., Construction of crystalline 2D covalent organic frameworks with remarkable chemical (acid/base) stability via a combined reversible and irreversible route. J. Am. Chem. Soc. 134, 19524-19527 (2012). https://doi.org/10.1021/ja308278w
32.	Y. Liang, M. Xia, Q. Yu, Y. Li, Z. Sui et al., Guanidinium-based ionic covalent organic frameworks for capture of uranyl tricarbonate. Adv. Compos. Hybrid Mater. 5, 184-194 (2022). https://doi.org/10.1007/s42114-021-00311-3
33.	M.K. Hota, S. Chandra, Y. Lei, X. Xu, M.N. Hedhili et al., Electrochemical thin-film transistors using covalent organic framework channel. Adv. Funct. Mater. 32, 2201120 (2022). https://doi.org/10.1002/adfm.202201120
34.	X. Chen, Y. Li, L. Wang, Y. Xu, A. Nie et al., High-lithium-affinity chemically exfoliated 2D covalent organic frameworks. Adv. Mater. 31, e1901640 (2019). https://doi.org/10.1002/adma.201901640
35.	X. Xu, Z. Zhang, R. Xiong, G. Lu, J. Zhang et al., Bending resistance covalent organic framework superlattice: “nano-hourglass” -induced charge accumulation for flexible in-plane micro-supercapacitors. Nano-Micro Lett. 15, 25 (2022). https://doi.org/10.1007/s40820-022-00997-0
36.	Y. Yang, C. Zhang, Z. Mei, Y. Sun, Q. An et al., Interfacial engineering of perfluoroalkyl functionalized covalent organic framework achieved ultra-long cycled and dendrite-free lithium anodes. Nano Res. 16, 9289-9298 (2023). https://doi.org/10.1007/s12274-023-5534-0
37.	J. He, N. Wang, Z. Yang, X. Shen, K. Wang et al., Fluoride graphdiyne as a free-standing electrode displaying ultra-stable and extraordinary high Li storage performance. Energy Environ. Sci. 11, 2893-2903 (2018). https://doi.org/10.1039/C8EE01642A
38.	X. Wu, S. Xia, Y. Huang, X. Hu, B. Yuan et al., High-performance, low-cost, and dense-structure electrodes with high mass loading for lithium-ion batteries. Adv. Funct. Mater. 29, 1903961 (2019). https://doi.org/10.1002/adfm.201903961
39.	F. Yuan, W. Song, D. Zhang, Y.-S. Wu, Z. Li et al., Semi-ionic C-F bond inducing fast ion storage and electron transfer in carbon anode for potassium-ion batteries. Sci. China Mater. 66, 2630-2640 (2023). https://doi.org/10.1007/s40843-022-2419-4
40.	X. Wang, H. Hao, J. Liu, T. Huang, A. Yu, A novel method for preparation of macroposous lithium nickel manganese oxygen as cathode material for lithium ion batteries. Electrochim. Acta 56, 4065-4069 (2011). https://doi.org/10.1016/j.electacta.2010.12.108
41.	X. Xu, C. Qi, Z. Hao, H. Wang, J. Jiu et al., The surface coating of commercial LiFePO₄ by utilizing ZIF-8 for high electrochemical performance lithium ion battery. Nano-Micro Lett. 10, 1 (2018). https://doi.org/10.1007/s40820-017-0154-4
42.	X. Li, M. Sun, C. Xu, X. Zhang, G. Wang et al., Fast kinetic carbon anode inherited and developed from architectural designed porous aromatic framework for flexible lithium ion micro capacitors. Adv. Funct. Mater. 33, 2300460 (2023). https://doi.org/10.1002/adfm.202300460
43.	S. Zheng, J. Ma, Z.-S. Wu, F. Zhou, Y.-B. He et al., All-solid-state flexible planar lithium ion micro-capacitors. Energy Environ. Sci. 11, 2001-2009 (2018). https://doi.org/10.1039/C8EE00855H
44.	X. Yan, Y. He, X. Liu, S. Jing, J. Guan et al., Deterministic effect of the solid-state diffusion energy barrier for a charge carrier on the self-discharge of supercapacitors. ACS Energy Lett. 8, 2376-2384 (2023). https://doi.org/10.1021/acsenergylett.3c00453

Please choose a citation manager

Content to export