Exploring metal organic frameworks for energy storage in batteries and supercapacitors
TL;DR: In this paper, the authors review and comment on recent progress in metal-organic framework-based lithium-ion batteries, sodium-ion battery, lithium-air battery, and supercapacitors.
About: This article is published in Materials Today.The article was published on 2017-05-01 and is currently open access. It has received 358 citations till now. The article focuses on the topics: Electrochemical energy conversion & Supercapacitor.
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TL;DR: An overview of the energy storage devices from conventional capacitors to supercapacitors to hybrid systems and ultimately to batteries is provided, although the focus is kept on capacitive and hybrid energy storage systems.
Abstract: Over the past decade, electrochemical energy storage (EES) devices have greatly improved, as a wide variety of advanced electrode active materials and new device architectures have been developed. These new materials and devices should be evaluated against clear and rigorous metrics, primarily based on the evidence of real performances. A series of criteria are commonly used to characterize and report performance of EES systems in the literature. However, as advanced EES systems are becoming more and more sophisticated, the methodologies to reliably evaluate the performance of the electrode active materials and EES devices need to be refined to realize the true promise as well as the limitations of these fast-moving technologies, and target areas for further development. In the absence of a commonly accepted core group of metrics, inconsistencies may arise between the values attributed to the materials or devices and their real performances. Herein, we provide an overview of the energy storage devices from conventional capacitors to supercapacitors to hybrid systems and ultimately to batteries. The metrics for evaluation of energy storage systems are described, although the focus is kept on capacitive and hybrid energy storage systems. In addition, we discuss the challenges that still need to be addressed for establishing more sophisticated criteria for evaluating EES systems. We hope this effort will foster ongoing dialog and promote greater understanding of these metrics to develop an international protocol for accurate assessment of EES systems.
695 citations
TL;DR: This review focuses on the design and fabrication of one-, two- and three-dimensional MOFs at micro/nanoscale, and their direct applications in batteries, supercapacitors and electrocatalysis.
Abstract: As a new class of crystalline porous materials, metal-organic frameworks (MOFs) have received great attention owing to their unique advantages of ultrahigh surface area, large pore volume and versatile applications. Developing different strategies to control the morphology and size of MOFs is very important for their practical applications. Recently, micro/nanosized MOFs have been regarded as promising candidates for electrode materials with excellent performances, which not only bridge the gap between fundamental MOF science and forward-looking applications, but also provide an opportunity to make clear the relationship between morphologies and properties. This review focuses on the design and fabrication of one-, two- and three-dimensional MOFs at micro/nanoscale, and their direct applications in batteries, supercapacitors and electrocatalysis. A discussion on challenges and future prospects of the synthesis and electrochemical applications of micro/nanoscaled MOF materials is presented.
615 citations
26 Jul 2019
TL;DR: In this paper, the authors provide an overview of selected metal organic frameworks (MOFs) attributes for applications in solid-state electrolytes and battery operation in extreme environments, and provide an updated account on MOFs employed in batteries and supercapacitors.
Abstract: Metal-organic frameworks (MOFs) are a class of porous materials with unprecedented chemical and structural tunability. Their synthetic versatility, long-range order, and rich host–guest chemistry make MOFs ideal platforms for identifying design features for advanced functional materials. This review addresses synthetic approaches to control MOF attributes for realizing material properties such as charge conductivity, stability, surface area, and flexibility. Along with an updated account on MOFs employed in batteries and supercapacitors, new directions are outlined for advancing MOF research in emergent technologies such as solid-state electrolytes and battery operation in extreme environments. Synthetic tenability of metal organic frameworks renders them versatile platform for next-generation energy storage technologies. Here the authors provide an overview of selected MOF attributes for applications in solid-state electrolytes and battery operation in extreme environments.
495 citations
01 Jul 2019
TL;DR: In this article, a review of metal-organic frameworks (MOFs) derived nanomaterials for various electrochemical energy storage and conversion applications including Li-ion batteries, Li-S batteries, Na-ion battery, supercapacitors, water splitting, and oxygen reduction reaction is reviewed.
Abstract: As emerging crystalline porous organic-inorganic hybrid materials, metal-organic frameworks (MOFs) have been widely used as sacrificial precursors for the synthesis of carbon materials, metal/metal compounds, and their composites with tunable and controllable nanostructures and chemical compositions for electrochemical energy applications. Herein, recent progress of MOF-derived nanomaterials for various electrochemical energy storage and conversion applications including Li-ion batteries, Li-S batteries, Na-ion batteries, supercapacitors, water splitting, and oxygen reduction reaction is reviewed. Structural and compositional design of MOF-derived nanomaterials is systematically summarized, which may hopefully offer inspirations and guidances for future development of MOF-derived nanomaterials for more efficient and more durable electrochemical energy applications.
424 citations
TL;DR: In this paper, a review of hierarchical porous carbons for supercapacitors is presented, where the authors introduce different pore types and define hierarchical porous structures, followed by discussion and exemplification of major synthesis strategies.
Abstract: Carbon materials, owing to their excellent electrical conductivity, tailorability, inexpensiveness and versatility, have been extensively studied as electrode materials for supercapacitors. The capacitance of carbon-based supercapacitor electrodes has remained at a mediocre level between 100 and 200 F g−1 for decades. Until recently, a new family of carbon materials termed hierarchical porous carbons has pushed the capacitance to new benchmark values beyond 300 F g−1, and has revitalized the exploration of carbon materials for supercapacitors. Hierarchical porous carbons contain different scales of pores (from micropores to macropores) inter-connected together and assembled in hierarchical patterns. Experimental studies coupled with theoretical investigations have elucidated that the presence of micropores is responsible for offering a large surface area to enhance charge storage capability, whilst mesopores, macropores and the hierarchical structure improve electrolyte infiltration and facilitate ion diffusion. This review will start by introducing different pore types and the definition of hierarchical porous structures, followed by discussion and exemplification of major synthesis strategies. In addition, recent molecular-level understanding of the relationship between pore size, functionalities inside pores, pore spatial distribution and capacitive performance is presented. Finally, challenges and future opportunities associated with hierarchical porous carbons for supercapacitors are discussed.
419 citations
References
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TL;DR: In this paper, the authors reviewed the challenges for further development of Li rechargeable batteries for electric vehicles and proposed a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital and highest occupied molecular orbital (HOMO) or a constituent that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery.
Abstract: The challenges for further development of Li rechargeable batteries for electric vehicles are reviewed. Most important is safety, which requires development of a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) or a constituent (or additive) that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery. A high Li-ion conductivity (σ Li > 10 ―4 S/cm) in the electrolyte and across the electrode/ electrolyte interface is needed for a power battery. Important also is an increase in the density of the stored energy, which is the product of the voltage and capacity of reversible Li insertion/extraction into/from the electrodes. It will be difficult to design a better anode than carbon, but carbon requires formation of an SEI layer, which involves an irreversible capacity loss. The design of a cathode composed of environmentally benign, low-cost materials that has its electrochemical potential μ C well-matched to the HOMO of the electrolyte and allows access to two Li atoms per transition-metal cation would increase the energy density, but it is a daunting challenge. Two redox couples can be accessed where the cation redox couples are "pinned" at the top of the O 2p bands, but to take advantage of this possibility, it must be realized in a framework structure that can accept more than one Li atom per transition-metal cation. Moreover, such a situation represents an intrinsic voltage limit of the cathode, and matching this limit to the HOMO of the electrolyte requires the ability to tune the intrinsic voltage limit. Finally, the chemical compatibility in the battery must allow a long service life.
8,535 citations
TL;DR: This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorbents in rigid and flexible MOFs, and primary relationships between adsorptive properties and framework features are analyzed.
Abstract: Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).
7,186 citations
TL;DR: New strategies are needed for batteries that go beyond powering hand-held devices, such as using electrode hosts with two-electron redox centers; replacing the cathode hosts by materials that undergo displacement reactions; and developing a Li(+) solid electrolyte separator membrane that allows an organic and aqueous liquid electrolyte on the anode and cathode sides, respectively.
Abstract: Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid–solution range. The solid–solution range, which is...
6,950 citations
TL;DR: Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups and can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl.
Abstract: A strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that allowed the design of porous structures in which pore size and functionality could be varied systematically. Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups –Br, –NH2, –OC3H7, –OC5H11, –C2H4, and –C4H4 and that its pore size can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. We synthesized an isoreticular series (one that has the same framework topology) of 16 highly crystalline materials whose open space represented up to 91.1% of the crystal volume, as well as homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. One member of this series exhibited a high capacity for methane storage (240 cubic centimeters at standard temperature and pressure per gram at 36 atmospheres and ambient temperature), and others the lowest densities (0.41 to 0.21 gram per cubic centimeter) for a crystalline material at room temperature.
6,922 citations
TL;DR: Li-ion battery technology has become very important in recent years as these batteries show great promise as power sources that can lead us to the electric vehicle (EV) revolution as mentioned in this paper.
Abstract: Li-ion battery technology has become very important in recent years as these batteries show great promise as power sources that can lead us to the electric vehicle (EV) revolution. The development of new materials for Li-ion batteries is the focus of research in prominent groups in the field of materials science throughout the world. Li-ion batteries can be considered to be the most impressive success story of modern electrochemistry in the last two decades. They power most of today's portable devices, and seem to overcome the psychological barriers against the use of such high energy density devices on a larger scale for more demanding applications, such as EV. Since this field is advancing rapidly and attracting an increasing number of researchers, it is important to provide current and timely updates of this constantly changing technology. In this review, we describe the key aspects of Li-ion batteries: the basic science behind their operation, the most relevant components, anodes, cathodes, electrolyte solutions, as well as important future directions for R&D of advanced Li-ion batteries for demanding use, such as EV and load-leveling applications.
5,531 citations