Nickel-based pillared MOFs for high-performance supercapacitors: Design, synthesis and stability study
Introduction
Supercapacitors (SCs) have attracted increasing attention as novel energy storage devices due to their higher power densities, faster charge-discharge rates, and longer cycling lives than conventional rechargeable batteries [1], [2], [3]. According to the physicochemical processes responsible for energy storage, SCs are generally classified into (i) electrical double layer capacitors (EDLCs) where the energy storage is associated with charge separation within double layers (e.g. porous carbon materials [4], [5]) and (ii) pseudocapacitors which utilize near-surface redox reactions of transition metal oxides and hydroxides materials [6], [7], [8]. In general, EDLCs offer a very high charge/discharge rate with a long cycle life but have low capacitance, while pseudocapacitors have high capacitance but slightly inferior rate capability and cycling life [4], [5], [6], [7], [8].
To narrow the performance gap between these two types of capacitors, rational design of advanced electrode materials is necessary. Metal organic frameworks (MOFs) are drawing much attention as a potential electrode candidate for SCs [9], [10], [11], [12], [13], [14], [15], [16], [17] due to their remarkable surface areas, facile tunable pore size, and peculiar structures with potential pseudo-capacitive redox centers [17] either utilized as porous metal oxides [9], [10], porous carbon templates [11], [12], [13] or in a direct application as a new type of electrode material [14], [15], [16]. However, the instability of most MOFs or MOF-derived electrode material during charge-discharge process is widely considered a major limitation for their application in SCs [18].
To achieve an improved cycling performance, we tried to synthesize kinetically stable MOFs via ligand functionalization. Our previous work demonstrates that it is possible to adjust the water stability of pillared MOFs both in the positive and negative directions by proper functionalization of the BDC ligand [19], [20], [21]. Notably, placing nonpolar groups (e.g., -methyl) on the BDC linker leads to enhanced stability of DMOF, while placing polar groups (e.g., –OH) on the BDC linker has no such effect on the structure compared to the original one. Besides, Tan et al. [22] also found the stability of different metal based isostructural DMOFs [M(BDC)(DABCO)0.5] follows the order of Cu-DMOF<Ni-DMOF>Zn-DMOF>Co-DMOF which corresponds to the bond dissociation energy of diatomic molecules metal–oxygen and overall formation(stability) constants of metal amine complexes.
Herein, we summarized previous results [19], [20], [21], [22] and synthesized nickel-based, pillared MOFs of similar topology using 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (TM), 1,4-naphthalenedicarboxylic acid (NDC) and 9,10-anthracenedicarboxylic acid (ADC) as carboxylate ligands and 1,4-diazabicyclo[2.2.2]octane (DABCO) as pillar ligands and have successfully confirmed the water stability of Ni-DMOF-ADC and Ni-DMOF-TM. When used as electrodes for SCs, the Ni-DMOF-ADC derived highly functionalized nickel hydroxide electrode inherited the high stability of DMOF-ADC and showed excellent cycling performance, the capacitance retention after 16,000 cycles at 10 A g−1 was >98%, which was much higher than that of the relatively less stable Ni-DMOF-TM and the unstable Ni-DMOF-NDC derived electrodes. These results indicate the impact of DMOFs' structure stability on long-term cycling stability and show that water stable DMOFs could be a promising electrode material for long cycle-life electrochemical capacitors.
Section snippets
Synthesis of DMOF
The Ni-DMOF-ADC was synthesized by using a simple solvothermal method modified from literature [23]. All the chemicals were commercially available and used as obtained without further purification. Typically, 1 mmol of Ni(NO3)2·6H2O, 1 mmol of ADC, and 0.5 mmol of DABCO were dissolved in 10 mL of DMF at room temperature in a glass beaker and the resulting slurry was stirred for 2 h. After filtering the solution, the filtrate was poured into a Teflon-lined stainless steel reactor and kept in a
Characteristics of Ni-DMOFs
The crystallinity and purity of the prepared DMOF samples was confirmed by comparing with simulated patterns from single crystal X-ray diffraction (Fig. S1, Supporting information). Similarities among all the patterns were evident; these frameworks are isostructural to the simulated pattern, suggesting that all the MOFs probably had a layered topology (CCDC no. 992483) which can be described as metal paddle-wheel clusters connected by functionalized BDC ligands to form 2-D layers that are
Conclusions
In summary, we have synthesized novel isostructural nickel-based, pillared MOFs with different kinetic water stability based on our previous systematic study and applied them to supercapacitor electrode. Our study shows that the electrode made from the most stable Ni-DMOF-ADC had better electrochemical results in terms of specific capability and rate performance than the other two, and exceptional cyclic stability (98% after 16,000 cycles) compared to other electrochemical studies based on MOFs
Acknowledgments
This work was supported by the Center for “Understanding and Control of Acid Gas-induced Evolution of Materials for Energy”, an Energy Frontier Research Center funded by DOE, Office of Science, BES under Award #DESC0012577 and by a DOE ARPA-E project under Award number DE-AR0000303. C.Q. thanks for a fellowship from China Scholarship Council (No. 201406010208).
Chong Qu is currently a Ph.D. candidate under supervision of Prof. Ruqiang Zou, Peking University. He received his bachelor degree from School of Chemistry and Chemical Engineering at Nanjing University in 2013. He joined Prof. Meilin Liu’s group as a GT-PKU joint program student at School of Materials Science and Engineering, Georgia Institute of Technology in 2014. His research interests include electrochemical materials based on crystalline porous frameworks for supercapacitors and Li-ion
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Chong Qu is currently a Ph.D. candidate under supervision of Prof. Ruqiang Zou, Peking University. He received his bachelor degree from School of Chemistry and Chemical Engineering at Nanjing University in 2013. He joined Prof. Meilin Liu’s group as a GT-PKU joint program student at School of Materials Science and Engineering, Georgia Institute of Technology in 2014. His research interests include electrochemical materials based on crystalline porous frameworks for supercapacitors and Li-ion battery.
Yang Jiao was born and raised in Tianjin, China. In 2012, he received his bachelor degree in Chemical Engineering from Tianjin University, China. He is currently a Ph.D. candidate in Professor Krista Walton’s research laboratory at the Georgia Institute of Technology. His current research focus is to understand and enhance the performance of metal–organic frameworks in acid gas environments and experimental synthesis and design of nanoporous materials for supercapacitors and Li-ion battery applications.
Bote Zhao is currently a post-doctoral fellow at the School of Materials Science and Engineering at Georgia Institute of Technology, USA. He received his B.S. and Ph.D. from Nanjing Tech University, China. His research experiences include work with binder-free films, nanostructured materials and graphene based materials for lithium-ion batteries and supercapacitors as well as the electrospinning synthesis of fibers, fabrication and water management of proton exchange membrane fuel cells, and hydrogen production from hydrous hydrazine. He is currently focusing on the synthesis and characterization of novel materials for batteries, fuel cells, and supercapacitors.
Dongchang Chen received his bachelor degree from department of chemical physics at University of Science and Technology of China in 2011. He is currently a Ph.D. candidate under supervision of Prof. Meilin Liu at School of Materials Science and Engineering, Georgia Institute of Technology. His research interests mainly focus on insitu spectroscopic study of solution-based electrochemical reactions.
Ruqiang Zou is currently the Professor of Materials Science and Engineering at the College of Engineering, Peking University. He received his Ph.D. from Kobe University and the National Institute of Advanced Industrial Science and Technology (AIST), Japan under the supervision of Professor Qiang Xu. His research interests focus on the controllable preparation of nanoporous materials for green energy utilization. He proposed a new strategy to construct hierarchically porous materials for single molecule adsorption, and extended their potential applications in hydrogen storage, carbon capture, and energy storage materials.
Krista Walton was born in Florence, Alabama, and grew up in nearby Elgin. She received a B.S.E. degree from the University of Alabama—Huntsville and Ph.D. from Vanderbilt University, both in chemical engineering. She joined the faculty of the Georgia Institute of Technology in the School of Chemical & Biomolecular Engineering in August 2009 and is now Associate Professor and Marvin R. McClatchey and Ruth McClatchey Cline Faculty Fellow. Her research involves the design and synthesis of next-generation multifunctional, porous materials for adsorption applications.
Meilin Liu is a Regents' Professor of Materials Science and Engineering and Co-Director of the Center for Innovative Fuel Cell and Battery Technologies at Georgia Institute of Technology, Atlanta, Georgia, USA. He received his BS from South China University of Technology and both MS and Ph.D. from University of California at Berkeley. His research interests include insitu/operando characterization and multi-scale modeling of charge and mass transfer along surfaces, across interfaces, and in membranes, thin films, and nanostructured electrodes, aiming at achieving rational design of materials and structures with unique functionalities for efficient energy storage and conversion.
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These authors contributed equally to this work.