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Application of Bimetallic MOFs and Their Derivatives in Electrochemical Energy Storage

Yumeng Wang , Rong Yang , Qijiu Deng , Chaojiang Fan , Suzhen Zhang , Yinglin Yan

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 460 -473.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 460-473 DOI: 10.7536/PC201113
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Application of Bimetallic MOFs and Their Derivatives in Electrochemical Energy Storage
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Abstract

Bimetallic organic frameworks and their derivatives have the characteristics of rich pore structure, large specific surface area, adjustable structure, abundant active sites, as well as the synergistic effect between bi-component and porous structure, so they are paid close attention to by researchers and widely used in electrochemical energy storage, catalysis, separation, sensors, medicine, gas storage and other fields. Just as monometallic organic frameworks, the poor conductivity and collapsible structure of bimetallic organic frameworks greatly limit their applications in electrochemical energy storage. It is through heat treatment of bimetallic organic frameworks that porous carbon@bimetallic oxide/sulfide/phosphide/selenide derivatives with uniform distribution, which not only keep rich pore structure, but also have improved conductivity and structural stability, being conducive to the application in the field of electrochemical energy storage are obtained. Therefore, in the view of the main metal ions in the bimetallic organic frameworks, this research reviewes the latest progress of the organic frameworks and their derivatives in electrochemical energy storage devices such as supercapacitors, lithium ion batteries, sodium ion batteries, and metal-air batteries, respectively. On this basis, the advantages of bimetallic MOFs in the application of electrochemical energy storage are summarized, and suggestions on its preparation, mechanism and post-treatment are put forward.

Contents

1 Introduction

2 Application of bimetallic MOFs in the field of electrochemical energy storage

2.1 Co-based bimetallic MOFs

2.2 Ni-based bimetallic MOFs

2.3 Zn-based bimetallic MOFs

2.4 Other bimetallic MOFs

3 Conclusion and outlook

Graphical abstract

Keywords

bimetallic organic framework / derivatives / electrochemical energy storage

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Yumeng Wang, Rong Yang, Qijiu Deng, Chaojiang Fan, Suzhen Zhang, Yinglin Yan. Application of Bimetallic MOFs and Their Derivatives in Electrochemical Energy Storage. Progress in Chemistry, 2022, 34(2): 460-473 DOI:10.7536/PC201113

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1 Introduction

With the development of society, energy shortage and environmental problems have become a great challenge facing mankind[1,2]. In response to the energy crisis, wind, solar, tidal and other renewable energy have been widely developed and utilized, but the characteristics of intermittent power generation limit their practical application and sustainable development. In recent years, more and more attention has been paid to the newly developed electrochemical energy storage and conversion technologies, such as supercapacitors, secondary batteries and solar cells, which are considered to be an effective way to store and utilize these clean energy sources[3]. Supercapacitors (SCs) have high power density, good safety and good cycle stability, but low energy density[4⇓⇓⇓⇓~9]. Lithium-ion batteries (Lithium ion battery, LIBs) have high theoretical capacity and energy density, but low power density, which can not meet the future market demand[10]. According to its working principle, its performance mainly depends on the physical and electrochemical properties of the electrode material[3]. Metal-air batteries are known as "green energy for the 21st century" because of their high energy density, high cost performance, stable performance, long life and pollution-free, but their commercialization process largely depends on the development of low-cost, high-performance oxygen reduction/oxygen evolution reaction (ORR/OER) electrocatalysts (Figure 1)[11⇓⇓~14]. In order to make up for the shortcomings of these energy storage devices and improve their practicability, researchers have tried to use various materials as their electrodes or catalysts, and metal-organic frameworks and their derivatives are one of them.
Metal-Organic Frameworks (MOFs) are coordination polymers self-assembled by multidentate Organic ligands containing oxygen, nitrogen, etc. And transition Metal ions, which have the characteristics of high porosity, large specific surface area, diverse structures and unsaturated metal sites, and have great application prospects in the field of energy storage[15]. However, most MOFs have poor conductivity and unstable structure, which make it difficult to be directly applied to energy storage devices. Pyrolysis of MOFs to form different nanostructured derivatives may be a practical strategy to address the above obstacles. Since Liu et al reported the first MOFs-derived porous carbon materials, various porous carbon materials, metal oxides, metal sulfides, metal phosphides and their composites have emerged in an endless stream, which has promoted the research and development of energy storage materials to a certain extent[16][17][18][19][20][21]. In the process of research, it is found that the application of monometallic MOFs in energy storage devices is limited, while the construction of bimetallic MOFs can effectively utilize the advantages of each monometallic MOF, and even produce special synergistic effects, thus improving the physical and electrochemical properties of materials. On the one hand, this is conducive to the application of bimetallic MOFs in energy storage devices, on the other hand, it is conducive to obtaining derivatives with excellent performance, such as heat treatment of bimetallic MOFs, which can easily complete the carbonization of organic ligands and oxidation/sulfurization/phosphide/selenization of bimetal (Table 1).O as to obtain atom-level uniformly distributed porous carbon @ bimetallic oxide/sulfide/phosphide/selenide and other derivatives, greatly improve the specific surface area, the conductivity and the structural stability of the material, and provide a new idea for preparing uniformly distributed bimetallic oxide/sulfide/phosphide/selenide @ porous carbon and the like.
The commonly used monometallic MOFs for electrochemical energy storage are mainly transition metal MOFs such as cobalt, nickel and zinc, and most bimetallic MOFs are also synthesized and studied on the basis of these MOFs.Therefore, this paper introduces the latest application progress of bimetallic MOFs and their derivatives in electrochemical energy storage from the main metal ions in bimetallic MOFs, namely cobalt-based, nickel-based, zinc-based and other bimetalic MOFs.

2 Application of Bimetallic MOFs in Electrochemical Energy Storage

2.1 Cobalt-based bimetallic MOFs

ZIF-67 is one of the most common cobalt-based MOFs, with regular morphology, simple preparation method and mild conditions. Therefore, most cobalt-based bimetallic MOFs are obtained on the basis of ZIF-67. For example, Kong et al. prepared a layered ZnCo-ZIF by using a cation exchange strategy to exchange part of the Co2+ with a zinc nitrate solution to etch the ZIF- 67 precursor, and its derivatives performed well as supercapacitor electrodes[22]. The research of Li et al shows that cobalt has a certain catalytic effect on the graphitization of amorphous carbon in the carbonization process of MOFs, and can promote the formation of graphitic carbon and carbon nanotubes, thereby improving the conductivity of materials, which is conducive to the application of cobalt-based MOFs in the field of electrochemical energy storage[23].

2.1.1 Supercapacitor

At present, there are two main ways to make bimetallic MOFs directly used in supercapacitors: one is to grow MOFs directly on the current collector in situ, and the other is to compound them with highly conductive substances. Seo et al. prepared Co/Mn-MOF @ nickel foam composites by immersing nickel foam in the precursor solution and then hydrothermal reaction, in which MOF nanoparticles were in direct contact with the current collector, providing favorable conditions for the rapid diffusion of ions[24]. The highest energy density of the constructed Co/Mn-MOF//activated carbon (AC) hybrid supercapacitor is up to 57.2 Wh·kg-1. Guan et al. prepared CoSx/Ni-Co-LDH bicomponent nanocages by using a multi-step transformation method: firstly synthesizing ZIF-67, then adding nickel ions for etching and precipitation after partial sulfurization[25]. The nanocage consists of a hollow rhombic dodecahedron, in which CoSx with a lower energy bandgap improves the conductivity of the material. The CoSx/Ni-Co-LDH electrode can provide a specific capacitance of 1562 F·g-1 at a current density of 1 A·g-1, and the capacity retention of the assembled CoSx/Ni-Co-LDH//AC hybrid supercapacitor is 94.56% after 10,000 cycles. This provides a good direction for further research on the direct application of metal-organic frameworks in supercapacitors.
At present, most studies focus on the application of MOFs derivatives in energy storage devices, and heat treatment is one of the simplest and most efficient methods to obtain MOFs derivatives. Saleki et al. calcined CoCu-ZIF in air to prepare CuCo2O4 material (ZCCO) with double-layer hollow sphere structure, which has 93 m2·g-1 specific surface area, short ion transmission path and abundant accessible active centers due to its hollow structure[30]. It has 701 C·g-1 ultra-high specific capacity at 2 A·g-1, and the capacity retention rate is more than 93.6% after 6000 times of charge and discharge. The highest energy density of the ZCCO//rGO hybrid supercapacitor is 38.4 Wh·kg-1, and the highest power density is 16 kW·kg-1, which is comparable to that of the MH-Ni battery.
Compositing MOFs with carbon materials can effectively improve the conductivity, inhibit agglomeration and improve the electrochemical performance. As shown in Fig. 2, Liu et al. uniformly loaded NiCo-MOF on eggplant carbon (EC) by hydrothermal method, and then vulcanized it in sodium sulfide solution to obtain EC@NiCo2S4 composite, in which the theoretical content of NiCo2S4 was 93.8%[44]. The EC@NiCo2S4 composite exhibits a high specific capacitance of 1394.5 F·g-1 at 1 A·g-1, which is four times higher than that of EC(327 F·g-1), and also exhibits excellent rate capability and high cycling stability with a capacity retention of 124% after 10,000 cycles. The reasons for the excellent electrochemical performance are, on one hand, the flaky morphology, oxygen-rich and nitrogen-rich surfaces, and ultra-high specific surface area of EC are crucial for the separation of NiCo2S4 nanosheets, and on the other hand, the hydrothermal process leads to the coordination of Ni2+ and Co3+ with carbon polar groups, which limits the growth of NiCo2S4 nanosheets on carbon sheets and enriches their pore structures.
The electrochemical properties of supercapacitors assembled with cobalt-based bimetallic MOFs and their derivatives are summarized in Table 2. They generally have excellent cycle performance and high energy density, which make up for the low energy density of supercapacitors. In addition, by comparison, it is found that cobalt-based bimetallic MOFs derived bimetallic sulfides used in supercapacitors can significantly improve their specific capacity, which provides a new idea for the study of supercapacitor electrode materials with high specific capacity.

2.1.2 Lithium-ion battery

MOFs-derived metal oxides and their composites are widely used in LIBs due to their low and flat charge-discharge plateau, high capacity and stable cycle performance[34,49]. Zhao et al. prepared ZnO/Co3O4/CoO/Co composites by heat treatment of ZnCo-ZIF in air and used them as LIBs anode materials[50]. The porous composite showed excellent cycling performance with a specific capacity of 681.2 mAh·g-1 after 1000 cycles and a retention of 74.7% compared with the second discharge. The excellent lithium storage performance, good cycle stability and rate capability of the material are attributed to the synergistic effect of the porous structure and the multi-component functional micro/nano particle system.
Bimetallic ZIF-67 can be treated to obtain a variety of hollow/core-shell derivatives, which is beneficial to improve the specific surface area and shorten the ion transport path. Duan et al. prepared bimetallic phosphide (NiCoP) nanocages by phosphating NiCo-ZIF-67 with NaH2PO2·H2O during heat treatment[41]. As shown in Fig. 3, the NiCoP nanocage well inherits the quasi-polyhedral morphology of the ZIF-67 precursor. Its inner and outer layers are composed of many interconnected nanosheets, with a large number of micropores on the surface. The nanosheets are cross-connected to form a unique multi-channel framework, which is conducive to the rapid diffusion of ions and electrons. The NiCoP electrode was used as the negative electrode of LIBs with high reversible capacity, high rate capability and good cycling stability. Their excellent electrochemical performance is related to the following factors: (1) large specific surface area, large number of holes and short ion migration path; (2) the porous channel structure enhances electrical contact and accommodates large volume changes; (3) that bimetallic phosphide enhance the conductivity; (4) The nanocage structure reduces the diffusion stress, which is beneficial to the penetration of electrolyte and provides conditions for the rapid transfer of electrons and ions. The unique three-dimensional structure and excellent electrochemical performance of NiCoP have broad application prospects in the field of LIBs, and this strategy for the preparation of hollow nanocages can also be applied to the preparation of other electrode materials.
Wei et al. used ZnCo-ZIF-67 as a precursor to prepare a zinc-cobalt bimetallic sulfide @ nitrogen-doped carbon composite (Zn-Co-S @ N-C) with a yolk-shell structure by mixing with sulfur powder under nitrogen protection and heat treatment[38]. The composite is composed of a Zn-Co-S "yolk" with an average size of about 90 nm and a N-doped carbon "eggshell" with a thickness of about 15 nm. The unique porous yolk shell structure shortens the Li+/e- diffusion distance and provides enough space to accommodate the volume change during the Li+ insertion/extraction process. The presence of N-doped carbon matrix not only enhances the electron transfer kinetics, but also improves the stability of the structure. More importantly, the two metal sulfides have different Li+ intercalation/deintercalation potentials. During the charge-discharge process, only one component participates in the electrochemical reaction at a specific voltage, and the other inactive component can be regarded as a buffer material to alleviate the large volume change, thus enhancing the lithium storage performance. In addition, the calculation shows that the introduction of Zn reduces the formation of by-products, thereby improving the electrochemical performance of the material. The Zn-Co-S @ N-C electrode exhibits good cycling stability, rate capability, and high coulombic efficiency of more than 96%. Wu et al. prepared Co-BTC by microwave irradiation, converted Co-BTC into Co-Cu-BTC by cation exchange, and annealed in air to obtain Co3O4@CuO microspheres with yolk-shell structure, and then modified the surface with carboxylated graphene quantum dots (GQDs) to obtain Co3O4@CuO@GQDs[34]. As shown in Figure 4 (B), when it is used as the negative electrode of LIBs, the specific capacity is 816 mAh·g-1 after 200 cycles at 0.1 A·g-1, which benefits from the larger specific surface area and more active sites provided by the GQDs coating, and more importantly, the unique stepwise lithium storage mechanism of the bimetallic oxide microspheres with yolk-shell structure (first in CuO shell,Then in the Co3O4 core), the mesoporous structure and the high porosity provide large specific surface area and abundant active centers, which are helpful to the diffusion of electrolyte and Li+, and can accommodate the volume change of the electrode in the charging and discharging process, so that the lithium storage performance is greatly improved, and the discharge capacity and cycle stability are excellent.

2.1.3 Metal-air battery

At present, the research on metal-air battery mainly focuses on the development of low-cost and high-performance ORR/OER electrocatalysts, among which MOFs is a typical representative, whose porous structure and abundant active sites are conducive to the improvement of battery performance. Chao et al. Prepared a series of M-FeCo-ZIFs-X frameworks (X is the molar ratio of Fe/Co) by template method, and then prepared M-FeCo-N-C-X molecular sieve catalysts with micro-mesoporous structure by heat treatment using M-FeCo-ZIFs-X as precursor[13]. When M-FeCo-N-C-X was used as the cathode catalyst for lithium-oxygen batteries, it was found that the M-FeCo-N-C-0.2-based cathode had a high initial capacity of 18 750 mAh·g-1, good rate capability, and cycle stability at 0.1 A·g-1, which was superior to most non-noble metal catalysts. The reasons for the excellent performance mainly include: (1) The morphology and micro-mesoporous structure of the precursor are retained, in which the micropores not only have a strong ability to capture oxygen, but also promote the nucleation and early deposition of Li2O2, and the mesopores provide channels for the wetting of the electrolyte; (2) The abundant nitrogen-doped carbon can effectively optimize the local electronic structure and improve the ORR activity; (3) Fe/Co can serve as an OER catalytic active site to enhance the charge transfer from Li2O2 to metal (Fe/Co), thereby further decomposing Li2O2. In summary, the synergistic effect of its hierarchical porous structure with high catalytic activity greatly improved the performance of Li-O2 cells (Figure 5).
Pendashteh et al. Synthesized CoFe-MOF by solvothermal method on the basis of ZIF-9, and achieved the purpose of high iron doping without changing its crystal structure[28]. They further prepared Co/Fe/N Co-doped bimetallic carbon by pyrolysis, in which uniformly distributed Fe/Co provided sufficient active sites, and nitrogen doping was beneficial to the enhancement of ORR activity.ZIF-9 _ Fe3 _ Pyrol was assembled in a Zn-air battery with high capacity of 815 mAh·g-1 and energy density of 1018 Wh·kg-1, and the cycling stability was superior to the current state-of-the-art PtRuC supported air electrode, which is an excellent bifunctional catalyst.
In addition, cobalt-based bimetallic MOFs derivatives have also been used as cathode sulfur storage materials for lithium-sulfur batteries. Li et al. prepared Co0.75Ni0.25NC/CNTs/S on the basis of CoNi-MOF/CNTs, which was used as the cathode of lithium-sulfur battery, with the initial discharge capacity of 1320.8 mAh·g-1 at 0.1 C, good rate capability and high cycle stability of more than 200 times[51].
To sum up, cobalt-based bimetallic MOFs are difficult to be directly applied to electrochemical energy storage devices due to their poor conductivity, large steric hindrance and difficulty in electrolyte infiltration[52]. Many researchers choose to heat treat them, which not only retains the porous structure, but also achieves heteroatom doping during carbonization, thus obtaining derivatives with large specific surface area, high conductivity and good electrolyte wettability.However, the process of heat treatment is complex, time-consuming and laborious, and the cost is high. In the future, we may try to compound MOFs with other conductive substrates, or directly self-assemble MOFs into functional devices to solve these problems.

2.2 Nickel-based bimetallic MOFs

Monometallic Ni-based MOFs are mostly two-dimensional (2D) lamellar structures. Compared with most 2D materials, 2D-MOFs have diverse structures, high porosity and structural rigidity, which can provide abundant active sites and open pore structures, and are conducive to the application of 2D-MOFs and their derivatives in electrochemical energy storage[53][54]. Table 3 summarizes the micromorphologies of Ni-based bimetallic MOFs, most of which retain the characteristics of lamellar structure and have a certain degree of stacking.Special morphologies such as hydrangea shape, flower spike shape and bunch shape are generated, the specific surface area of the material is further improved, and derivatives prepared by using the material as a precursor also retain the special morphologies, so that the electrochemical performance of the material is superior[55][21][42].

2.2.1 Supercapacitor

In addition to the choice of electrode materials, the performance of supercapacitors largely depends on the surface morphology of the materials[13]. In order to realize the direct application of nickel-based bimetallic MOFs in supercapacitors, researchers have compounded them with nickel foam or conductive carbon materials. Wang et al. constructed a triangular NiCo-MOF nanosheet array on the surface of nickel foam (NF) through a one-step hydrothermal reaction, which was used as a battery-type electrode material for a hybrid supercapacitor with excellent rate capability and a specific capacity of 1413 F·g-1 at 10 A·g-1[56]. Kumaraguru et al. Prepared bimetallic Ni/Co-MOF and its composite with reduced graphene oxide (rGO) (Ni/Co-MOF/rGO) at room temperature[57]. Ni/Co-MOF is rod-like particles with a length of about 3 ~ 10 μm, which provides more electron transport paths, shortens the length of ion diffusion paths and improves the overall conductivity of the material. rGO is beneficial to the rapid transport of electrons and prevents the agglomeration of MOFs particles. Electrochemical performance tests show that the Ni/Co-MOF/rGO exhibits a high specific capacitance of 1162 F·g-1 and excellent cycling performance.
In addition to direct applications, most of the current studies use bimetallic MOFs as precursors to improve electrochemical performance while maintaining the structure through sulfidation/phosphation/selenylation processes. Li et al. prepared nitrogen-sulfur Co-doped bimetallic nanocomposites (NS-BNs) by calcination/sulfidation with thioacetamide (TAA) using Ni/Co-MOF as precursor[35]. The specific capacitance under the 1 A·g-1 reaches the specific capacitance under the 1529 F·g-1,10 A·g-1 and is still as high as 1069 F·g-1, showing superior rate performance. Zhou et al. Prepared bimetallic Ni/Co-MOF by heating reflux method, and then synthesized NiCoP/C nanohybrid materials by calcination/sodium dihydrogen hypophosphite phosphating method[40]. NiCoP nanoparticles uniformly embedded in a large amount of carbon can improve the conductivity of the composite (C: Ni or C: Co is about 50:8) and provide a fast channel for electron transfer; The introduction of Co makes the electrode structure more stable on the one hand, and improves the rate capability of the electrode on the other hand. The immobilization of metal phosphide by bimetal and carbon makes the sample have good electrochemical performance, which is much better than that of Ni2P/C and Co2P/C. Moreover, the constructed NiCoP/C//AC asymmetric supercapacitor has an energy density up to 47.6 Wh·kg-1 at a power density of 798.9 W·kg-1, which is superior to the previously reported Ni/Co phosphide nanomaterials[61,62]. Qu et al. Synthesized NiSe2/CoSe2 nanopolyhedra with hollow structure by selenization of sodium hydrogen selenide (NaHSe) using bimetallic NiCo-ZIF as precursor[63]. The hollow polyhedron structure of NiSe2/CoSe2 makes the material have sufficient active sites, large specific surface area and fast ion/electron diffusion channels, which effectively improves the "dead volume" phenomenon (the penetration range of electrolyte from the surface to the inside of the electrode is generally about 20 nm.This means that the contribution of materials with a depth of more than 20 nm to electrochemical energy storage is negligible), which improves the utilization of electrode materials and endows Ni-Co-Se electrodes with outstanding electrochemical performance. The Ni-Co-Se electrode shows a high specific capacitance of 1668 F·g-1 and excellent rate capability at 1 A·g-1.

2.2.2 Lithium-ion battery

Nickel-based bimetallic MOFs used for LIBs mostly need to improve their electrochemical performance through sulfidation/phosphation/selenization processes. Wang et al. obtained a highly efficient multifunctional electrode material (NiS2/FeS2/NC) by carbonizing and sulfidizing rod-like bimetallic Ni/Fe-MOF[59]. Among them, NiS2/FeS2 nanoparticles with abundant defects and grain boundaries can provide abundant active sites and reduce the surface charge transfer resistance, thus improving the lithium storage performance. The three-dimensional nitrogen-doped carbon network improves the conductivity and specific surface area of the material, reduces the agglomeration of the NiS2/FeS2, and enables the material to be fully exposed to the electrolyte. Therefore, the LIBs test of NiS2/FeS2/NC shows high reversible capacity, good cycling performance and rate capability. In addition, NiS2/FeS2/NC nanorods are excellent in electrocatalysis. This work provides a new strategy for the design of highly efficient multifunctional electrode materials.
Wang et al. treated bimetallic NiCo-MOF @ graphene oxide by one-step carbonization/sodium dihydrogen hypophosphite phosphating method to obtain an excellent LIBs anode material (Ni1.4Co0.6P/C@NGN)[64]. The bimetallic phosphide nanoparticles provide more active sites and more redox reactions, the graphene matrix provides a large specific surface area and a stable conductive network, and the MOFs-derived carbon limits the volume expansion of phosphides, avoids mechanical crushing and maintains stability. The hybrid electrode fabricated using Ni1.4Co0.6P/C@NGN exhibits high specific capacity, excellent rate capability, and excellent cycling stability.
Yang et al. First synthesized 3D NiCo-MOF with layered bundle micro/nanostructures at room temperature[42]. The Ni-Co-Se @ C composite material is obtained through one-step carbonization/selenium powder selenization reaction. It inherits the bundle-like morphology of NiCo-MOF and has excellent cycling performance when used as the negative electrode of LIBs, with a reversible capacity greater than the theoretical value after 300 cycles. The Ni-Co-Se @ C electrode is characterized by the synergistic effect of the two metal selenides on lithium storage, a layered porous bundle-like structure, a stable carbon network, and a particle size reduction after the initial cycle. These characteristics not only reduce the volume change of metal selenides, but also provide more active sites and shorter lithium diffusion paths for lithium storage, promote the rapid transfer of charges and maintain a stable solid electrolyte interface film.

2.2.3 Metal-air battery

Li et al. prepared FeNi3Cx-Pdy nanorods using bimetallic Ni/Fe-MOF as a sacrificial precursor, which had high electrocatalytic activity as a bifunctional catalyst. In the OER test, the overpotential at 50 mA·cm-2 was only 288 mV, which was significantly better than that of RuO2 catalyst, and its catalytic ORR performance was also close to that of Pt/C catalyst[29]. When FeNi3Cx-Pd-7% is added as an air cathode catalyst in a zinc-air battery (RZAB), its power density is 234 mW·cm-2, energy density is about 967 Wh·kg-1, and specific capacity is 772 mAh·g-1. In addition, the long cycle life (more than 900 cycles) and the total overpotential of only 720 mV at 10 mA·cm-2 offer the potential for commercial application of RZAB (Figure 6).
Pourfarzad et al. Prepared bifunctional oxygen electrocatalyst Ni/Fe-BTC-MOF by electrochemical synthesis[60]. The unique rod-like morphology, the ultra-high specific surface area of 1943 m2·g-1, the porous structure and the covalent coordination of p and d orbitals between organic and inorganic substances in the lattice are beneficial to the diffusion of oxygen and electrolyte, and enhance the power and energy density, durability and stability of the catalyst. Electrochemical tests show that the Ni/Fe-BTC-MOF cathode has an open circuit potential of 1.55 V, a power density of 182 mW·cm-2, a large specific capacity of 775 mAh·g-1 at 10 mA·cm-2, and a good cycle life, which provides a reference for the development of the next generation of advanced green electrochemical energy storage technology.
In addition to the above electrochemical energy storage devices, nickel-based bimetallic MOFs also have some applications in other aspects. In order to improve the cycle stability of lithium-sulfur batteries and the specific capacity of sulfur cathode, Zhang et al. designed and synthesized a graphite-carbon-coated binary metal oxide composite (C/NCO) derived from NiCo-MOFs as a sulfur carrier for the cathode of lithium-sulfur batteries through a process of stirring at room temperature, air carbonization, and acid washing[58]. Acid washing dissolved some Co and Ni particles, decreased the mass density of C/NCO, and made C/NCO porous. Porous carbon and NiCo2O4 not only efficiently capture polysulfides by physical and chemical adsorption, but also serve as a highly conductive matrix for sulfur, facilitating the transport of electrons and Li+. The sulfur content in the C/NCO-450-A @ S electrode reaches 68.9 wt%, showing an initial capacity of 977 mAh·g-1 at 0.5 C and a high reversible capacity of 673 mAh·g-1 after 500 cycles, indicating a good cycling performance, which provides a feasible strategy to improve the performance of lithium-sulfur batteries.
The special morphology formed by stacking 2D sheets endows nickel-based bimetallic MOFs with large specific surface area and abundant active sites, and the derivatives obtained by subsequent treatment on the basis of which not only retain these advantages, but also have better conductivity and structural stability, which is conducive to their application in the field of electrochemical energy storage. However, it is difficult to prepare 2D sheet-like MOFs with the desired structure by using the existing preparation methods. Therefore, the preparation of Ni-based bimetallic MOFs with the desired structure in a highly controllable manner remains one of the major challenges in this field.

2.3 Zinc-based bimetallic MOFs

Zinc is the fourth "common" metal after iron, aluminum and copper, which is abundant and cheap, and the coordination of zinc ion is strong, so it is easy to form a variety of MOFs materials with organic ligands, the most common is ZIF-8 (metal center is Zn2+, ligand is 2-methylimidazole), and zinc-based bimetallic MOFs are mostly synthesized on the basis of ZIF-8. In addition, the melting point and boiling point of zinc are relatively low, which makes the organic ligands transform into porous carbon during the annealing process of zinc-based MOFs, and the evaporation of zinc produces a hierarchical microporous structure in porous carbon materials.It improves the specific surface area and porosity of the material, which is conducive to providing more active sites, improving the conductivity of the material and binding the active substances, so the bimetallic zinc-based MOFs derivatives have better electrochemical performance[23].

2.3.1 Supercapacitor

Some researchers have explored the heat treatment conditions of MOFs materials. Lei et al. used bimetallic ZnCo-MOF as a template to prepare nanoporous carbons (NPCs) by combining rapid heating and direct activation of CO2, and used them as electrode materials for supercapacitors[65]. As shown in Fig. 7, the NPCs have a large number of microporous structures with specific surface area up to 652.36 m2·g-1 and pore volume of 0.28 cm3·g-1, both larger than the common heating rate samples, resulting in higher specific capacitance and better rate capability. The specific capacitance of NPCs is still as high as 120 A·g-1 even at a high current density of 20.0 A·g-1, which indicates that the rapid heating and activation of MOFs precursors in CO2 atmosphere is an effective way to prepare supercapacitor electrode materials.
Samuel et al. Grown ZnMn-ZIF-8 nanoparticles directly on polyacrylonitrile nanofibers by electrospinning, and then carbonized them in air to obtain flexible dodecahedral nanoparticles modified carbon nanofibers (Mn @ ZnO/CNFs)[33]. The synergistic effect of the Mn @ ZnO faradaic reaction active centers on these composite fibers and the highly conductive carbon nanofibers improves the performance of the supercapacitor electrode. By optimizing the doping amount of Mn, the energy density of Mn @ ZnO/CNF electrode is 72.1 Wh·kg-1 and 33.3 Wh·kg-1 when the power density is 500 W·kg-1 and 5000 W·kg-1, respectively (Fig. 8).

2.3.2 Lithium-ion battery

Guo et al. prepared CoZnSx@ nitrogen-doped carbon by calcination/TAA solution sulfidation of 2D leaf-shaped ZnCo-ZIF precursor[39]. The calcined CoZnSx@ nitrogen-doped carbon can well maintain the complete shape of the 2D blade, provide a continuous electron transport channel, effectively shorten the ion/electron transport path, and inhibit the agglomeration of metal sulfides; Bimetallic sulfides can effectively alleviate the volume expansion during the charge-discharge process and improve the cycle stability through multi-step conversion reactions. The special structure of 2D nitrogen-doped carbon and the synergistic effect of bimetallic sulfides make it show excellent performance when used as LIBs anode, with a specific capacity of 527 mAh·g-1 and a Coulombic efficiency of about 99% after 200 cycles at a current density of 0.5 A·g-1.
Chen et al. prepared bifunctional ZnO-NiO microsphere electrode with yolk-shell structure by annealing the Zn[Ni(CN)4] precursor[18]. ZnO-NiO as LIBs anode exhibits high capacity and excellent cycling performance at 0. 25 C. When used as a supercapacitor electrode, it can provide high specific capacitance of 1350 F·g-1 when the current density is 3.0 A·g-1. The excellent electrochemical performance is attributed to the fact that zinc oxide and nickel oxide provide abundant active sites for the electrochemical reaction, and the yolk-shell structure effectively alleviates the volume expansion and structural collapse of the electrode during charge-discharge cycles. This work provides a new strategy for the design of highly efficient multifunctional electrode materials.

2.3.3 Metal-air battery

Zhu et al. loaded tubular ZnO @ Zn/Co-ZIF on carbon cloth by a two-step method, and then annealed to remove Zn to obtain hollow Co, N-Co-doped carbon nanotube electrode (HCA-Co)[27]. Because the hollow nitrogen-doped carbon nanotube is in direct contact with the carbon matrix, the ion diffusion path is short, and the fine Co nanoparticles ensure abundant reaction sites for rapid electrochemical reaction, the obtained flexible HCA-Co electrode has good catalytic performance for ORR and OER,When used as the air cathode of a binderless all-solid-state Zn-air battery, it has an open-circuit voltage of 1.40 V, a maximum power density of 44.8 mW·cm-3, good cycling stability, and mechanical flexibility, which are superior to those of common Pt/C-based devices. HCA-Co is also used as the cathode of solid aluminum batteries, which has higher open-circuit voltage and better mechanical flexibility than Pt/C electrode, and has broad application prospects in flexible electronic devices.
Zhang et al. reported a bimetallic ZnCo-ZIF based composite electrocatalyst (CNCo-N @ Fe-X), which consists of N mesoporous carbon nanotubes with high graphitization and uniform distribution of active sites (Co, Fe3C, N-C, Fe-Nx, and Co-Nx[66]. The experimental results showed that CNCo-5 exhibited similar ORR activity to that of Pt/C catalyst in alkaline medium, and the ORR performance, stability and methanol resistance of CNCo-5 @ Fe-2 were greatly improved by further doping with Fe3C, even exceeding those of Pt/C and most non-noble metal catalysts. The excellent ORR performance of CNCo-5 @ Fe-2 can be attributed to the synergistic effects of high porosity (efficient mass transfer and reduced volume change), large specific surface area (effective exposure of active sites and contact with electrolyte), one-dimensional structure with high graphitization degree (enabling rapid transport of reactants and products), and a large number of uniformly distributed active sites (enhancing catalyst activity). The combined effect of these factors makes CNCo-5 @ Fe-2 nanotubes show good performance when used in zinc-air batteries (Fig. 9).

2.3.4 Lithium-sulfur battery

MOFs and their derivatives used in lithium-sulfur batteries are mainly used as separator coatings or positive electrode sulfur storage materials to inhibit shuttle effect and improve battery capacity and cycle stability. Song et al. prepared three-dimensional network nanocomposite cobalt/nitrogen-doped carbon nanosheets/carbon nanotubes (Co/NCNS/CNT) by high-temperature calcination of ZnCo-MOF @ CNT[67]. The three-dimensional conductive network provides a fast electron transfer path, the Co/N Co-doping and nanosheet structure can quickly adsorb polysulfides, and the most important thing is that the uniformly distributed Co nanoparticles and Co — N — C bonds can catalyze the conversion of long-chain lithium polysulfides into short-chain lithium polysulfide, thereby improving the reaction kinetics and inhibiting the shuttle effect. When used as a separator coating for lithium sulfur batteries, the capacity decay rate is only 0.05% per cycle over 1000 long cycles.
Yu et al. reported a compact three-dimensional interconnected sulfur cathode based on ZnCo-ZIF with "three highs" (i.e., high areal sulfur loading, high electrode compactness, and high sulfur content),Its open-pore three-dimensional carbon network provides multi-dimensional electron and ion transport pathways and shortens the diffusion length, the intimate contact between sulfur and carbon matrix promotes the adsorption of polysulfides, and the Co nanoparticles catalyze the conversion process of polysulfides[68]. With a high areal sulfur loading of 10.9 mg·cm-2, a high sulfur content of 74 wt%, and a low electrolyte/sulfur ratio of 6μL·mg-1, it still exhibits a high capacity of 801 mAh·g-1 at a high rate of 0.5 C and retains 72.8% after 200 cycles. In addition, it can be cycled for 2000 cycles at an ultra-high rate of 10 C under an areal sulfur loading of 2.1 mg·cm-2, which provides a guiding example for the rational structural design of sulfur cathodes for lithium-sulfur batteries.
Zinc-based bimetallic MOFs also face the problems of poor conductivity, steric hindrance and difficulty in electrolyte wetting, so there are few reports on their direct application in electrochemical energy storage devices.However, after the removal of Zn by heat treatment, its derivatives have large specific surface area, rich pore structure, sufficient active sites and good conductivity, so the current research mainly focuses on its derivatives. In the future, if there is a better solution to solve the above problems, so that it can be directly applied to electrochemical energy storage devices, then zinc-based bimetallic MOFs and their derivatives will be more widely used in the field of electrochemical energy storage.

2.4 Other Bimetallic MOFs

In addition to the common cobalt/nickel/zinc-based bimetallic MOFs, other bimetallic MOFs (such as copper/manganese/iron) have gradually attracted people's attention. Rajpurohit et al. studied the supercapacitive properties of CuFe-MOF and its composite with sulfur-doped graphene (CuFeBTC/S-GNS)[69]. The presence of active sites in bimetallic MOFs and the excellent conductivity of S-GNS make it easier for electrolyte ions to penetrate into the active materials, resulting in high specific capacitance. The symmetrical supercapacitor assembled with this material can deliver energy and power densities of 96.57 Wh·kg-1 and 1595.12 W·kg-1 at an operating voltage of 1.8 V and a current density of 1.0 A·g-1, and the energy density is still as high as 50.20 Wh·kg-1 even at a current density of 20.0 A·g-1, indicating that CuFeBTC/S-GNS is a promising high-performance electrochemical energy storage material. Tijerina et al. Synthesized CuNi-MOF at room temperature to prepare copper-nickel bimetallic doped carbon-based materials (CuNi0.25@C and CuNi0.50@C,Ni:Cu molar ratios of 0.25 and 0.50, respectively) by pyrolysis[70]. As shown in Fig. 10, CuNix@C inherits the irregular porous surface of Cu-MOF and the bundle-like spike-type morphology of Ni-MOF, which is beneficial to the penetration of electrolyte, so that the redox reaction can occur faster. The electrochemical performance was tested by cyclic voltammetry, and the results show that the peak potential differences of CuNi0.25@C and CuNi0.5@C are 204 and 447 mV, respectively, which are lower than those of monometallic carbon materials, and may be suitable for the reduction electrode of I 3 - in solar cells.
Wang et al. prepared MnFe-PBA @ CNTs by a chemical precipitation method, and then fabricated them into MnSe/FeSe2 doped porous carbon nanotubes (Mn-Fe-Se/CNTs) by a one-step carbonization/selenization method[43]. The three-dimensional structure consists of spherical Mn-Fe-Se interlaced with CNTs. Each Mn-Fe-Se sphere consists of dozens of nanoparticles and many holes. The single nanoparticle is uniformly covered by a nitrogen-doped amorphous carbon layer. The Mn-Fe-Se/CNTs has a unique porous structure and the synergistic effect of multi-components, which makes it have good rate capability and cycle stability. When used in sodium-ion batteries (SIBs), it can still provide high capacity of 552 mAh·g-1 and good rate performance after 70 charge-discharge cycles; In addition, when used in potassium-ion batteries (PIBs), it also shows a high capacity of 351 mAh·g-1 and excellent rate performance. Guo et al. prepared MnO/ZnO/C by pyrolyzing bimetallic MnZn-MOF, which has excellent lithium storage capacity, the first discharge capacity reaches 1396 mAh·g-1 at 0.2 A·g-1, the initial coulombic efficiency is higher than 75%, and it still remains at 636 mAh·g-1 after 1000 cycles, showing excellent rate and cycle performance[71].
Xu et al. synthesized a graphene-supported Fe-Sn nanoalloy composite (FeSn2/FeSn/Fe-rGO) by the bimetallic MOFs precursor method[72]. The introduction of electrochemically inactive Fe can inhibit the agglomeration of Sn particles and buffer the volume change of the electrode, while rGO nanosheets can not only prevent the aggregation of Fe-Sn alloy, but also ensure the rapid electron transfer during the electrochemical process. The results show that the LIBs based on the FeSn2/FeSn/Fe-rGO composites have excellent lithium storage performance and excellent cycle stability within 1200 cycles at 2.0 A·g-1, and the capacity fading is only 0. 025% per cycle.
In addition to bimetallic MOFs, trimetallic MOFs have also attracted the attention of researchers. Cao et al. prepared a multi-component sulfide and nitrogen-doped carbon composite material (MnS- (ZnCo) S/N-C) with a porous hollow polyhedral structure by one-step solid state reaction using a trimetallic organic framework MnZnCo-TATB-MOFs as a precursor[73]. When used as an anode carrier for SIBs, it can still deliver a capacity of 316 mAh·g-1 after 400 cycles at 2.0 A·g-1, with a capacity retention of up to 92.9% compared with the third cycle. 40% capacity retention when the current is stepped up from 0.1 A·g-1 to 10.0 A·g-1. The synergistic effect of porous hollow polyhedral structure, nitrogen-doped carbon coating and multi-component sulfides is the reason for the excellent cycle performance of the composite at high current: the unique porous hollow structure inherited from the MOFs precursor particles not only has a large specific surface area, but also can withstand the volume expansion during charging and discharging; In-situ nitrogen doping as well as multi-component sulfides improved the conductivity and electrochemical activity of the material (fig. 11).

3 Conclusion and prospect

In this paper, the application progress of bimetallic MOFs and their derivatives in the field of electrochemical energy storage in recent years is reviewed. Their advantages mainly lie in: (1) relatively large specific surface area can increase the contact area between the electrode and the electrolyte, and promote the rapid transport of ions and electrons at the electrode/electrolyte interface; (2) the abundant pore structure is beneficial to relieving the volume change of the electrode and improving the cycle stability and safety of the electrochemical energy storage device; (3) Compared with monometallic MOFs, bimetallic MOFs and their derivatives provide more active sites and more abundant redox reactions, so that electrode reactions occur rapidly; (4) Bimetallic MOFs-derived porous carbon @ bimetallic oxide/sulfide/phosphide/selenide composites have large specific surface area, strong conductivity and good structural stability.Is beneficial to the application in the field of electrochemical energy storage, and simultaneously provides a new idea for preparing uniformly distributed bimetallic oxide/sulfide/phosphide/selenide and the like; (5) Bimetallic MOFs derivatives have strong electrocatalytic activity for ORR and OER reactions, and can be used as catalysts for metal-air batteries.
Although the applications of bimetallic MOFs and their derivatives in the field of electrochemical energy storage have emerged in an endless stream in recent years, there is still a lot of room for development. We believe that we can focus on the following aspects: (1) When used as electrode materials for supercapacitors and secondary batteries, the special morphology and porous structure of bimetallic MOFs and their derivatives are conducive to the improvement of electrochemical performance, but it is difficult to control the morphology and porous structure of bimetallic MOFs by existing preparation methods. The preparation of bimetallic MOFs with desired morphology and pore structure in a highly controllable way is still one of the main challenges in this field. (2) When used as catalysts for metal-air batteries, bimetallic or multimetallic MOFs usually show better electrochemical performance than monometallic MOFs, resulting in the effect of "1 + 1 > 2", that is, there is a "synergistic effect", but the mechanism of action has not been elaborated in the current published literature. If this phenomenon can be studied in depth, the material and morphological changes in the electrochemical reaction process can be analyzed by in-situ XRD/XPS/FT-IR/TEM techniques, and the mechanism can be explained systematically and comprehensively, then bimetallic and even multimetallic MOFs will be more widely used in the field of electrochemical energy storage. (3) The electrical conductivity of most bimetallic MOFs is poor, which can be significantly improved by heat treatment, but the heat treatment process may destroy the porous structure of MOFs itself, resulting in poor structural stability, and the mass loss of heat treatment process is large, resulting in low yield and high cost. The direct in-situ growth of MOFs on highly conductive substrates can not only improve the conductivity, but also inhibit the agglomeration of MOFs and improve the structural stability, which is a very effective means.
In conclusion, bimetallic MOFs-based materials have broad application prospects in the field of electrochemical energy storage. Although there are still many challenges in the research process, we believe that bimetallic MOFs are expected to play an important role in improving the performance of electrochemical energy storage devices, and this field deserves more efforts and attention.

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Funding

International Science and Technology Cooperation Program of China(2015DFR50350)

National Natural Science Foundation of China(51702256)

China Postdoctoral Science Foundation(2019M653706)

Innovation Capability Support Program of Shaanxi(2019TD-019)

Postdoctoral Science Foundation of Shaanxi Province of China(2018BSHEDZZ120)

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