Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance

Feng, Dawei; Lei, Ting; Lukatskaya, Maria R.; Park, Jihye; Huang, Zhehao; Lee, Minah; Shaw, Leo; Chen, Shucheng; Yakovenko, Andrey A.; Kulkarni, Ambarish; Xiao, Jianping; Fredrickson, Kurt; Tok, Jeffrey B.; Zou, Xiaodong; Cui, Yi; Bao, Zhenan

doi:10.1038/s41560-017-0044-5

Title: Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance

Journal Article · 01 January 2018 · Nature Energy

DOI: https://doi.org/10.1038/s41560-017-0044-5 · OSTI ID:1426494

Feng, Dawei ^[1];

^[1]; Lukatskaya, Maria R. ^[1]; Park, Jihye ^[1]; Huang, Zhehao ^[2];

^[1];

^[1]; Chen, Shucheng ^[1]; Yakovenko, Andrey A. ^[3]; Kulkarni, Ambarish ^[4]; Xiao, Jianping ^[4]; Fredrickson, Kurt ^[4]; Tok, Jeffrey B. ^[1]; Zou, Xiaodong ^[2]; Cui, Yi ^[5]; Bao, Zhenan ^[1]

Stanford Univ., CA (United States). Department of Chemical Engineering
Stockholm Univ. (Sweden). Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division, Advanced Photon Source
Stanford Univ., CA (United States). Department of Chemical Engineering, SUNCAT Center for Interface Science and Catalysis
Stanford Univ., CA (United States). Department of Materials Science and Engineering

For miniaturized capacitive energy storage, volumetric and areal capacitances are more important metrics than gravimetric ones because of the constraints imposed by device volume and chip area. Typically used in commercial supercapacitors, porous carbons, although they provide a stable and reliable performance, lack volumetric performance because of their inherently low density and moderate capacitances. In this paper, we report a high-performing electrode based on conductive hexaaminobenzene (HAB)-derived two-dimensional metal-organic frameworks (MOFs). In addition to possessing a high packing density and hierarchical porous structure, these MOFs also exhibit excellent chemical stability in both acidic and basic aqueous solutions, which is in sharp contrast to conventional MOFs. Submillimetre-thick pellets of HAB MOFs showed high volumetric capacitances up to 760 F cm^-3 and high areal capacitances over 20 F cm^-2. Furthermore, the HAB MOF electrodes exhibited highly reversible redox behaviours and good cycling stability with a capacitance retention of 90% after 12,000 cycles. In conclusion, these promising results demonstrate the potential of using redox-active conductive MOFs in energy-storage applications.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES); Knut and Alice Wallenberg Foundation; Swedish Research Council (SRC)

Grant/Contract Number:: AC02-76SF00515; AC02-06CH11357

OSTI ID:: 1426494

Alternate ID(s):: OSTI ID: 1461332

Journal Information:: Nature Energy, Vol. 3, Issue 1; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 687 works

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Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio Shen, Yuxia; Shan, Bohan; Cai, Hui Advanced Materials, Vol. 30, Issue 52 https://doi.org/10.1002/adma.201802497	journal	November 2018
Freestanding Lamellar Porous Carbon Stacks for Low‐Temperature‐Foldable Supercapacitors Yang, Yu; Ng, Sze‐Wing; Chen, Dongdong Small, Vol. 15, Issue 48 https://doi.org/10.1002/smll.201902071	journal	July 2019
Synthetic Strategies for Constructing Two-Dimensional Metal-Organic Layers (MOLs): A Tutorial Review: Synthetic Strategies for Constructing Two-Dimensional Metal-Organic Layers (MOLs): A Tutorial Review Cao, Lingyun; Wang, Tingting; Wang, Cheng Chinese Journal of Chemistry, Vol. 36, Issue 8 https://doi.org/10.1002/cjoc.201800144	journal	June 2018
Metal−Organic Frameworks for High‐Energy Lithium Batteries with Enhanced Safety: Recent Progress and Future Perspectives Zhang, Xiahui; Dong, Panpan; Song, Min‐Kyu Batteries & Supercaps, Vol. 2, Issue 7 https://doi.org/10.1002/batt.201900012	journal	April 2019
How to efficiently utilize electrode materials in supercapattery? Chen, Kunfeng; Xue, Dongfeng Functional Materials Letters, Vol. 12, Issue 01 https://doi.org/10.1142/s1793604718300050	journal	January 2019
Conductive Metal–Organic Frameworks Selectively Grown on Laser‐Scribed Graphene for Electrochemical Microsupercapacitors Wu, Hao; Zhang, Wenli; Kandambeth, Sharath Advanced Energy Materials, Vol. 9, Issue 21 https://doi.org/10.1002/aenm.201900482	journal	April 2019
A One‐Dimensional π–d Conjugated Coordination Polymer for Sodium Storage with Catalytic Activity in Negishi Coupling Chen, Yuan; Tang, Mi; Wu, Yanchao Angewandte Chemie International Edition, Vol. 58, Issue 41 https://doi.org/10.1002/anie.201908274	journal	September 2019
Fully Conjugated Phthalocyanine Copper Metal–Organic Frameworks for Sodium–Iodine Batteries with Long‐Time‐Cycling Durability Wang, Faxing; Liu, Zaichun; Yang, Chongqing Advanced Materials, Vol. 32, Issue 4 https://doi.org/10.1002/adma.201905361	journal	December 2019
Synthesis and solar cell application of a Ti (metal)-organic framework/carbon nanotube composite Sharma, Sandeep Kumar; Kumar, Kamal; Paul, A. K. Materials Research Express, Vol. 6, Issue 12 https://doi.org/10.1088/2053-1591/ab5752	journal	November 2019
Solid–solid interface growth of conductive metal–organic framework nanowire arrays and their supercapacitor application Du, Xing; Zhang, Jianing; Wang, Huali Materials Chemistry Frontiers, Vol. 4, Issue 1 https://doi.org/10.1039/c9qm00527g	journal	January 2020
Sodium-coupled electron transfer reactivity of metal–organic frameworks containing titanium clusters: the importance of cations in redox chemistry Saouma, Caroline T.; Tsou, Chih-Chin; Richard, Sarah Chemical Science, Vol. 10, Issue 5 https://doi.org/10.1039/c8sc04138e	journal	January 2019
Ultrathin two-dimensional π–d conjugated coordination polymer Co ₃ (hexaaminobenzene) ₂ nanosheets for highly efficient oxygen evolution Li, Chun; Shi, Lingling; Zhang, Lili Journal of Materials Chemistry A, Vol. 8, Issue 1 https://doi.org/10.1039/c9ta10644h	journal	January 2020
A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity Yao, Ming‐Shui; Zheng, Jia‐Jia; Wu, Ai‐Qian Angewandte Chemie International Edition, Vol. 59, Issue 1 https://doi.org/10.1002/anie.201909096	journal	January 2020
Secondary‐Component Incorporated Hollow MOFs and Derivatives for Catalytic and Energy‐Related Applications Yang, Haozhou; Wang, Xun Advanced Materials, Vol. 31, Issue 38 https://doi.org/10.1002/adma.201800743	journal	July 2018
Robust heterostructures of a bimetallic sodium–zinc metal–organic framework and reduced graphene oxide for high-performance supercapacitors Rajak, Richa; Saraf, Mohit; Mobin, Shaikh M. Journal of Materials Chemistry A, Vol. 7, Issue 4 https://doi.org/10.1039/c8ta09528k	journal	January 2019
A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction Zhong, Haixia; Ly, Khoa Hoang; Wang, Mingchao Angewandte Chemie, Vol. 131, Issue 31 https://doi.org/10.1002/ange.201907002	journal	July 2019
Nano-sandwiched metal hexacyanoferrate/graphene hybrid thin films for in-plane asymmetric micro-supercapacitors with ultrahigh energy density He, Yafei; Zhang, Panpan; Wang, Mao Materials Horizons, Vol. 6, Issue 5 https://doi.org/10.1039/c9mh00063a	journal	January 2019
Synergistic effects of engineered spinel hetero-metallic cobaltites on electrochemical pseudo-capacitive behaviors Lee, Young-Woo; Hong, John; An, Geon-Hyoung Journal of Materials Chemistry A, Vol. 6, Issue 31 https://doi.org/10.1039/c8ta04616f	journal	January 2018
Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks Rubio‐Giménez, Víctor; Almora‐Barrios, Neyvis; Escorcia‐Ariza, Garin Angewandte Chemie International Edition, Vol. 57, Issue 46 https://doi.org/10.1002/anie.201808242	journal	November 2018
Electroactive Metalorganic Frameworks Medina, Dana D.; Mähringer, Andre; Bein, Thomas Israel Journal of Chemistry, Vol. 58, Issue 9-10 https://doi.org/10.1002/ijch.201800110	journal	October 2018
Catalytic Metal Nanoparticles Embedded in Conductive Metal–Organic Frameworks for Chemiresistors: Highly Active and Conductive Porous Materials Koo, Won‐Tae; Kim, Sang‐Joon; Jang, Ji‐Soo Advanced Science, Vol. 6, Issue 21 https://doi.org/10.1002/advs.201900250	journal	August 2019
Core–shell assembly of carbon nanofibers and a 2D conductive metal–organic framework as a flexible free-standing membrane for high-performance supercapacitors Zhao, Shihang; Wu, Huihui; Li, Yanli Inorganic Chemistry Frontiers, Vol. 6, Issue 7 https://doi.org/10.1039/c9qi00390h	journal	January 2019
2D molecular crystal lattices: advances in their synthesis, characterization, and application Solomos, Marina A.; Claire, F. James; Kempa, Thomas J. Journal of Materials Chemistry A, Vol. 7, Issue 41 https://doi.org/10.1039/c9ta06534b	journal	January 2019
Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds Xie, Jiaze; Boyn, Jan-Niklas; Filatov, Alexander S. Chemical Science, Vol. 11, Issue 4 https://doi.org/10.1039/c9sc04381k	journal	January 2020
Recent Development and Application of Conductive MOFs Li, Pengfei; Wang, Bo Israel Journal of Chemistry, Vol. 58, Issue 9-10 https://doi.org/10.1002/ijch.201800078	journal	August 2018
Theoretical Investigation of 2D Conductive Microporous Coordination Polymers as Li-S Battery Cathode with Ultrahigh Energy Density Gao, Guoping; Zheng, Fan; Pan, Feng Advanced Energy Materials, Vol. 8, Issue 25 https://doi.org/10.1002/aenm.201801823	journal	July 2018
Morphology-dependent third-order optical nonlinearity of a 2D Co-based metal–organic framework with a porphyrinic skeleton Niu, Ru-Jie; Zhou, Wen-Fa; Liu, Yan Chemical Communications, Vol. 55, Issue 33 https://doi.org/10.1039/c9cc01363f	journal	January 2019
Titelbild: A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity (Angew. Chem. 13/2020) Jiang, Qiang; Xiong, Peixun; Liu, Jingjuan Angewandte Chemie, Vol. 132, Issue 13 https://doi.org/10.1002/ange.202001277	journal	January 2020
A Phthalocyanine-Based Layered Two-Dimensional Conjugated Metal-Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction Zhong, Haixia; Ly, Khoa Hoang; Wang, Mingchao Angewandte Chemie International Edition, Vol. 58, Issue 31 https://doi.org/10.1002/anie.201907002	journal	July 2019
Strain Redistribution in Metal‐Sulfide‐Composite Anode for Enhancing Volumetric Lithium Storage Xie, Dong; Yuan, Yingdong; Xiao, Li ChemElectroChem, Vol. 5, Issue 24 https://doi.org/10.1002/celc.201801254	journal	October 2018
Graphene-like metal-organic frameworks: Morphology control, optimization of thin film electrical conductivity and fast sensing applications Hoppe, Bastian; Hindricks, Karen D. J.; Warwas, Dawid P. Cambridge : Royal Society of Chemistry https://doi.org/10.15488/4168	other	January 2018
Conductive Co-based metal–organic framework nanowires: a competitive high-rate anode towards advanced Li-ion capacitors Sun, Jinfeng; Guo, Lingzhi; Sun, Xuan Journal of Materials Chemistry A, Vol. 7, Issue 43 https://doi.org/10.1039/c9ta08788e	journal	January 2019
Interweaving metal–organic framework-templated Co–Ni layered double hydroxide nanocages with nanocellulose and carbon nanotubes to make flexible and foldable electrodes for energy storage devices Xu, Chao; Kong, Xueying; Zhou, Shengyang Journal of Materials Chemistry A, Vol. 6, Issue 47 https://doi.org/10.1039/c8ta10133g	journal	January 2018
Hydrogen storage mechanism and diffusion in metal–organic frameworks Koizumi, Kenichi; Nobusada, Katsuyuki; Boero, Mauro Physical Chemistry Chemical Physics, Vol. 21, Issue 15 https://doi.org/10.1039/c8cp07467d	journal	January 2019
Synaptic Plasticity and Filtering Emulated in Metal–Organic Frameworks Nanosheets Based Transistors Ding, Guanglong; Yang, Baidong; Zhou, Kui Advanced Electronic Materials, Vol. 6, Issue 1 https://doi.org/10.1002/aelm.201900978	journal	November 2019
Porous Ultrathin NiSe Nanosheet Networks on Nickel Foam for High‐Performance Hybrid Supercapacitors Yu, Dengfeng; Li, Zhuo; Zhao, Gongyuan ChemSusChem, Vol. 13, Issue 1 https://doi.org/10.1002/cssc.201901766	journal	October 2019
Engineering Bimetal Synergistic Electrocatalysts Based on Metal–Organic Frameworks for Efficient Oxygen Evolution Liu, Ming; Kong, Lingjun; Wang, Xuemin Small, Vol. 15, Issue 45 https://doi.org/10.1002/smll.201903410	journal	September 2019
Interfacial Approach toward Benzene‐Bridged Polypyrrole Film–Based Micro‐Supercapacitors with Ultrahigh Volumetric Power Density Jiang, Kaiyue; Baburin, Igor A.; Han, Peng Advanced Functional Materials, Vol. 30, Issue 7 https://doi.org/10.1002/adfm.201908243	journal	December 2019
Interlayer Hydrogen‐Bonded Metal Porphyrin Frameworks/MXene Hybrid Film with High Capacitance for Flexible All‐Solid‐State Supercapacitors Zhao, Weiwei; Peng, Jiali; Wang, Weikang Small, Vol. 15, Issue 18 https://doi.org/10.1002/smll.201901351	journal	March 2019
Assembling laminated films via the synchronous reduction of graphene oxide and formation of copper-based metal organic frameworks Li, Li; Chen, Ruyi; Gong, Yujiao Journal of Materials Chemistry A, Vol. 7, Issue 1 https://doi.org/10.1039/c8ta09065c	journal	January 2019
Molecular understanding of charge storage and charging dynamics in supercapacitors with MOF electrodes and ionic liquid electrolytes Bi, Sheng; Banda, Harish; Chen, Ming Nature Materials, Vol. 19, Issue 5 https://doi.org/10.1038/s41563-019-0598-7	journal	February 2020
Shape‐Assisted 2D MOF/Graphene Derived Hybrids as Exceptional Lithium‐Ion Battery Electrodes Jayaramulu, Kolleboyina; Dubal, Deepak P.; Schneemann, Andreas Advanced Functional Materials, Vol. 29, Issue 38 https://doi.org/10.1002/adfm.201902539	journal	July 2019
Superior Electrochemical Performance of Pristine Nickel Hexaaminobenzene MOF Supercapacitors Fabricated by Electrophoretic Deposition Wechsler, S. C.; Amir, F. Z. ChemSusChem, Vol. 13, Issue 6 https://doi.org/10.1002/cssc.201902691	journal	March 2020
Two-dimensional metal–organic frameworks and their derivatives for electrochemical energy storage and electrocatalysis Zhao, Kuangmin; Zhu, Weiwei; Liu, Suqin Nanoscale Advances, Vol. 2, Issue 2 https://doi.org/10.1039/c9na00719a	journal	January 2020

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