MOF-Based Materials for Cathode Preparation in AZIBs: Comparison
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Please note this is a comparison between Version 2 by Dean Liu and Version 1 by Guobin Zhang.

Aqueous zinc-ion batteries (AZIBs) are promising for large-scale energy storage systems due to their high safety, large capacity, cost-effectiveness, and environmental friendliness. Their commercialization is currently hindered by several challenging issues, including cathode degradation and zinc dendrite growth.

  • metal-organic frameworks
  • MOF derivatives
  • aqueous zinc-ion batteries

1. Pure MOFs for Cathode Preparation

MOFs with high specific surface area and low density are promising electrode materials for AZIBs [47][1]. For instance, Prussian blue analogues (PBAs) are a type of coordination compound with a 3D open-framework structure, which can be described as MHCF (M are transition metal ions, and HCF means the hexacyanoferrate) [19][2]. According to the definition of MOFs, it is reasonable to classify PBAs as MOFs [48][3]. Zhang et al. synthesized rhombohedral zinc hexacyanoferrate (ZnHCF) and investigated its electrochemical properties as the cathode in AZIBs for the first time [49][4]. When the ZnHCF cathode was combined with a zinc anode, the full battery average operating voltage was as high as 1.7 V. Galvanostatic measurements displayed that the ZnHCF cathode can deliver a capacity of 65.4 mAh g−1 at 60 mA g−1 and good stability with a capacity retention of over 81% at 300 mA g−1. Through XPS and ex situ XRD techniques, the intercalation of Zn2+ ions into ZnHCF was verified. These key results pave the way for the further exploration of MOF-based cathodes in AZIBs. Moreover, a conductive two-dimensional MOF Cu3(HHTP)2 (HHTP is 2,3,6,7,10,11-hexahydroxytriphenylene) was designed by Nam and coworkers [50][5]. The electrical conductivity (0.2 S cm−1) and large one-dimensional channels (pores of ~2 nm) that existed in Cu3(HHTP)2 can fasten the diffusion of electron and Zn2+ ion to active sites and reduce interfacial impedance. The charge/discharge curves demonstrated that the Cu3(HHTP)2 cathode displayed a high reversible capacity of up to 228 mAh g−1 at 50 mA g−1 and outstanding capacity retention of 75% after 500 cycles at a high current density of 4 A g−1. Furthermore, the capacitive currents contribution of Cu3(HHTP)2 obtained by CV measurements was 83%, indicating that the Cu3(HHTP)2 follows an intercalation pseudocapacitance charge storage mechanism. In addition, Pu et al. synthesized five various MOF materials (denoted as Mn(BTC), Mn(BDC), Fe(BDC), Co(BDC), and V(BDC)) and systematically evaluated their electrochemical behaviors as the cathodes of AZIBs [51][6]. The charge/discharge curves revealed that Mn(BTC) exhibited the highest Zn2+ storage capacity of 112 mAh g−1 at a current of 50 mA g−1. Characterized by XRD, SEM, XPS, and FTIR, the transformation from Mn(BTC) to Zn(BTC) was observed during the first charge process while the Mn2+ ions dissolved into aqueous electrolytes and were oxidized to MnO2 on the cathode surface, serving as a host for Zn2+ and H+ storage in the following charge/discharge processes. Interestingly, rod-like Zn(BTC) was beneficial to the ion diffusion and cycle life. By adding MnSO4 to the ZnSO4 electrolyte, the resultant battery showed a long cycle life with 92% capacity retention after 900 cycles at 1000 mA g−1. Moreover, a particular type of V-MOF (MIL-47, VIV(O)(bdc)) featuring a one-dimensional layered nanorod-like framework was fabricated by Ru et al. via a facile one-pot hydrothermal method [52][7]. The as-prepared V-MOF was equipped with an enormous number of empty channels, which enabled it to increase the reaction active sites and boosted Zn2+ insertion and extraction. The assembled Zn//V-MOF battery delivered a specific discharge capacity of 332.3 mAh g−1 at 0.1 A g−1. Obviously, assorted pure MOFs as cathode materials show discrepant specific capacity by matching different metal clusters and organic ligands, the appropriate pairing needs to be further explored.
Additionally, it is worth mentioning that there are some optimization designs on the inner structure of pure MOFs to improve their electrochemical activity. Succeeding the research of Pu and coworkers mentioned above, Yin et al. innovatively demonstrated the idea of coordinately unsaturated Mn(BTC) as the cathode candidate of AZIBs [53][8]. By adjusting the Mn and −COOH with the molar ratio of 1.32:4, the optimal Mn-H3BTC-MOF-4 contributed to efficient Zn2+ transport and electronic/ionic conductivity. As a result, it showed a high capacity of 138 mAh g−1 at 0.1 A g−1 and 6.5% capacity fading after 1000 cycles at 3 A g−1. Moreover, Zeng and coworkers rationally designed Co-substituted Mn-rich PBA hollow spheres (denoted as CoMn-PBA HSs) [54][9] and Cu-substituted Mn-PBA double-shelled nanoboxes (denoted as CuMn-PBA DSNBs) [55][10] through an ion exchange approach. On the one hand, the unique hollow structure of materials exposed rich active sites, which alleviated the volume change during cycle performance. On the other hand, partial metal ions substitution might inhibit the Jahn–Teller distortions of Mn-N6 octahedra, thus contributing to the prolonged lifespan. The as-prepared CoMn-PBA HSs cathode exhibited a high reversible capacity of 128.6 mAh g−1 at 50 mA g−1. Similarly, the CuMn-PBA DSNBs cathode delivered a capacity of 116.8 mAh g−1 at 0.1 A g−1. Moreover, the exposed facet regulation of Ni-based MOF (PFC-8) was proposed by Yang et al. through a thermally modified strategy [56][11]. Generally, the PFC-8 was dominated by the exposed (110) facet [57][12]. After being heated to 350 °C and cooled down to room temperature, XRD characterization identified that (200) and (020) facets of PFC-8 350 increased significantly, which was favorable for specific capacity and electrochemical kinetics on account of (200) and (020) facets having double the Ni sites (acting as the active sites) than (110) facets. Consequently, the PFC-8 350 cathode achieved a superior discharge capacity of 110.0 mAh g−1 at 30 A g−1 while the PFC-8 cathode was 29.7 mAh g−1. As discussed above, pure MOFs with fascinating morphology and pore characteristics dramatically improve the electrochemical performance of AZIBs. Nevertheless, several disadvantages curtail the future development of pure MOFs, such as poor electric conductivity and structural instability. The poor electrical conductivity is an intrinsic consequence of how MOFs are typically constructed and structural instability results from their collapse under harsh charge/discharge conditions. To tackle these issues, MOF derivatives have been extensively considered as cathode materials for AZIBs, such as porous carbon materials, metal oxides, and their compounds.

2. MOF-Derived Carbon Materials for Cathode Preparation

Carbon materials such as carbon nanotubes (CNTs) [58[13][14],59], carbon fiber [60,61][15][16], and graphite/graphene [62,63][17][18] can effectively improve the electrochemical performance of electrode active materials. Among them, CNTs have a dense tube wall structure and slender tube diameter structure, which largely restrict the effective diffusion and electron transmission of internal active materials and electrolyte ions [64][19]. Therefore, Chai et al. in situ obtained a type of hierarchically porous hollow carbon nanostraw (denoted as HCNS) via facile pyrolysis and thermal reduction in an indium-based organic framework InOF-1 [65][20]. Compared with traditional CNTs, the MOF-derived HCNS stored more charge active sites and shortened ion transport pathways, which was favorable for better electrochemical exchange capacity. As a consequence, the zinc–iodine batteries assembled with as-synthesized HCNS displayed a maximum discharge capacity of 295.7 mAh g−1 at 0.5 A g−1 and a high Coulombic efficiency (87% after 1500 cycles) at 1 A g−1. In addition, carbon materials are widely used in MOF compounds such as MnO/C@rGO [66][21], MnO2/CC [67][22], and V2O5@C [68][23], which is beneficial to enhance the electrical conductivity of composite cathode materials. However, these pristine carbon materials only provide limited physical trappings of active materials. Instead, MOF-derived carbon materials with suitable size and exceptionally large surface areas provide a great possibility to mitigate the shuttle effect by chemically interacting active materials with higher binding energies, which contribute to the superior electrochemical performance of electrodes.

3. MOF-Derived Metal Oxides for Cathode Preparation

Traditional metal oxides, such as V2O5, and MnO2, have been extensively investigated as cathodes for AZIBs because of their high theoretical capacity. However, severe structural degradation of these materials limited their zinc storage capacity and rate capability. MOF-derived metal oxides with large specific surface areas and sufficient electrochemical active sites are feasible cathode materials. For instance, α-Mn2O3 was explored as a cathode of AZIBs by Mao and coworkers through the Mn-BTC-derived method [69][24]. TEM image showed that α-Mn2O3 exhibited rod-like morphology, consisting of nanoparticles with a diameter of about 100 nm, which boosted the contact between the cathode and electrolyte for fast ion diffusion. When assembled as a Zn/α-Mn2O3 battery, it obtained a high specific capacity of 225 mAh g−1 at 0.05 A g−1. Impressively, ithis work  pointed out the relationship between the charge storage mechanism of the α-Mn2O3 cathode and discharge current density. At lower current densities, the H+ and Zn2+ were intercalated cooperatively, while the H+ intercalation occurred dominantly at higher current densities. Additionally, MOF-derived V2O3 [70][25], ZnMn2O4/Mn2O3 [71][26], and Mn2O3/Al2O3 [72][27] were developed as well, and all of them enhanced the capacity and cycling stability of AZIBs successfully. Apparently, nanostructured MOF-derived metal oxides demonstrate significantly improved H+/Zn2+ storage performance as cathode materials compared with that of traditional metal oxides due to their unique structures, which provide abundant active sites and is favorable for excellent high capacity.

4. MOF Compounds for Cathode Preparation

MOF compounds can concoct pure MOFs, metal oxides, carbon materials, or other functional materials/groups together. This hybrid strategy can engender synergistic effects and optimize electrode performance to the maximum extent. For instance, a sandwich-like and alternately stacked Cu-HHTP and MXene heterostructure was designed by Wang et al. [42][28]. The Cu-HHTP/MX composite inherited advantages of both MOFs and MXene, which not only provided abundant active sites but also enhanced the electrical conductivity for effective charge transport. DFT calculations unraveled the highly reversible Zn2+ storage and zero-strain feature of the Cu-HHTP/MX heterostructure as the cathode for AZIBs. Significantly, the Cu-HHTP/MX cathode realized a high reversible specific capacity of 260.1 mA h g−1 at 0.1 A g−1. In addition, Tan et al. proposed a novel hydroxylation strategy for PBA manganese hexacyanoferrate (MnHCF) [73][29]. During the annealing engineering under the H2 atmosphere, an abundance of -OH functional groups preferred to settle on Mn atoms thanks to the lowest adsorption energy (about −4.14 eV) for -OH in Mn sites. Thus, OH-rich MnHCF can stimulate the Mn3+/Mn2+ and Fe3+/Fe2+ redox reaction, thereby enhancing electrochemical kinetics. Remarkably, an impressive discharge capacity of 136.1 mAh g−1 and a considerable energy density of 228.8 Wh kg−1 at 100 mA g−1 was achieved. Moreover, VPO4 was investigated as a cathodic material for AZIBs for the first time by Hwang et al. [74][30]. By carbonizing and phosphating MIL-47, high-crystallinity vanadium phosphate (denoted as HVPO) nanoparticles were in situ formatted. The electrically conductive carbon network not only contributed to the uniform interconnection of HVPO nanoparticles but also boosted charge transfer kinetics. During the electrochemical performance test, the HVPO cathode displayed a superior rate capability and ultra-stable capacity retention (almost no capacity fading at 10 A g−1 for 20,000 cycles). Moreover, Zhang et al. designed vanadium nitride-embedded nitrogen-doped carbon nanofiber (VN/N-CNFs) composites via an electrospinning technique [75][31]. Vanadium nitride (VN) can achieve a maximum of two-electron redox for vanadium atoms and a high theoretical specific capacity of up to 825 mAh g−1. By introducing MIL-47 as precursors, VN nanograins in situ grew and were homogeneously distributed into electrospun carbon nanofibers (CNFs). 3D self-supported skeletons and hierarchical structures were realized by this design strategy, which rendered a conductive layer and prevented VN nanograins from self-aggregation. Excitingly, the reversible capacity of VN/N-CNFs composites reached 734 mAh g−1 at 0.5 A g−1 and 482 mAh g−1 at 50 A g−1, and 297 mAh g−1 at a high rate of 100 A g−1. As described above, manifold MOF compounds were developed via matching assorted substances. Basically, MOF compounds as cathodes for AZIBs perform much better electrochemical behavior than their single components, shedding light upon an effective way toward superior aqueous zinc-ion batteries.

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