Recent Progress of Nanoscale Metal‐Organic Frameworks in Synthesis and Battery Applications

Abstract

As one type of promising inorganic–organic hybrid crystal material, metal‐organic frameworks (MOFs) have attracted widespread attention in many potential fields, particularly in energy storage and conversion. Recently, effective strategies have been developed to construct uniform nanoscale MOFs (NMOFs), which not only retain inherent advantages of MOFs but also develop some improved superiorities, including shorter diffusion pathway for guest transportation and more accessible active sites for surface adsorption and reaction. Additonally, their nanometer size provides more opportunity for post‐functionalization and hybridization. In this review, recent progress on the preparation of NMOFs is summarized, primarily through bottom‐up strategies including reaction parameter‐ and coordination‐assisted synthesis, and top‐down strategies such as liquid exfoliation and salt‐template confinement. Additionally, recent applications of NMOFs in batteries as electrodes, separators, and electrolytes is discussed. Finally, some important issues concerning the fabrication and application are emphasized, which should be paid attention in future.

Metal−Organic Frameworks: Why Make Them Small?

“…The larger contact areas and shorter path for transportation of mass, ions, and electrons provided by small MOFs can prove beneficial for practical and industrial applications such as energy storage. [ 36 ] For instance, Xiao et al, working on a MOF‐based anode for a lithium‐ion battery, reported that pulverization of ultrasmall sub‐5 nm Co‐MOF particles significantly increased the contact area between this MOF and the desired electrolyte, thereby shortening the electron and ion transport pathways (Figure 1c). [ 37 ] The authors were thus able to fabricate a battery showing excellent reversible capacity (1301 mAh g −1 at 0.1 A g −1 ), extraordinary rate performance (494 mAh g −1 at 40 A g −1 ), and outstanding cycling stability (98.6% capacity retention at 10 A g −1 after 2000 cycles), all far superior to those of other reported MOF‐based anodes for lithium‐ion batteries.…”

Recent Progress in Metal‐Organic Frameworks@Cellulose Hybrids and Their Applications

“…[ 1‐4 ] Compared with zeolites, active carbons, and mesoporous silicas, MOFs possess particular features, such as tunable structures, facile functionalization and incorporation of active sites. [ 5‐9 ] Thanks to these unique advantages, the application fields of MOFs cover gas storage/separation, [ 10‐13 ] catalysis, [ 14‐17 ] sensing, [ 18‐22 ] environmental remediation, [ 23‐27 ] proton conduction, [ 28‐31 ] energy storage, [ 32‐34 ] and even biomedical applications. [ 35‐38 ] Nevertheless, the large‐ scale commercialization of MOFs is seriously limited because of their intrinsic fragility, mechanical instability, and unworkability.…”

[Co3(μ3-O)]-Based Metal–Organic Frameworks as Advanced Anode Materials in K- and Na-Ion Batteries

“…However, MOFs have a poor electrical conductivity, which is harmful for electron transportation. Great efforts have been made to improve the electron conductivity of MOFs because pure MOFs anode materials are usually limited by poor electron conductivity, reversible capacities, and rate performances. − ,, Multifarious MOFs-based composite materials were explored in order to overcome the disadvantages of MOFs-based electrodes including carbon composite, metallic oxides, carbides, chalcogenides, phosphides, etc. − What is noteworthy is that mixing MOFs with single-walled carbon nanotubes (SWCNTs) is an efficient method to improve the performance in battery tests. The introduction of SWCNTs could solve the low conductivity of MOFs, and the construction of the cross-linked carbon network also shorten the ion diffusion pathways, which contributes to take full advantages of electroactive sites in MOFs.…”

“…Great efforts have been made to improve the electron conductivity of MOFs because pure MOFs anode materials are usually limited by poor electron conductivity, reversible capacities, and rate performances. [37][38][39]48,49 Multifarious MOFs-based composite materials were explored in order to overcome the disadvantages of MOFs-based electrodes including carbon composite, metallic oxides, carbides, chalcogenides, phosphides, etc. 50−54 What is noteworthy is that mixing MOFs with single-walled carbon nanotubes (SWCNTs) is an efficient method to improve the performance in battery tests.…”