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Application of Multi-Carbonyl Covalent Organic Frameworks in Secondary Batteries

Yi Zhang , Meng Zhang , Yifan Tong , Haixia Cui , Pandeng Hu , Weiwei Huang

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (11) : 2024 -2032.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (11) : 2024-2032 DOI: 10.7536/PC201002
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Application of Multi-Carbonyl Covalent Organic Frameworks in Secondary Batteries
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Abstract

Covalent organic frameworks(COFs) are a new kind of crystalline porous materials formed by covalent bonds of building units.With the feature of ultra-high porosity, stable framework structure, and excellent structural designability, COFs are considered to have great application prospects in secondary batteries. This article reviews the research progress of COFs containing multi-carbonyl building units(multi-carbonyl COFs, Mc-COFs) in different metal-ion secondary batteries, and the challenges faced by Mc-COFs as electrode materials and solid-state electrolyte materials are summarized. Additionally, the strategies for improving the battery performances are introduced in detail, and the development directions of Mc-COFs in secondary batteries are also prospected.

Contents

1 Introduction

2 Optimization of Mc-COFs electrode materials

2.1 Increase the active site

2.2 Improve active site utilization

2.3 Enhance the electronic transmission capability

3 Application of Mc-COFs in solid-state electrolytes

4 Conclusion and outlook

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Keywords

covalent organic frameworks / multi-carbonyl compounds / secondary batteries / electrode materials / solid-state electrolyte

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Yi Zhang, Meng Zhang, Yifan Tong, Haixia Cui, Pandeng Hu, Weiwei Huang. Application of Multi-Carbonyl Covalent Organic Frameworks in Secondary Batteries. Progress in Chemistry, 2021, 33(11): 2024-2032 DOI:10.7536/PC201002

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1 Introduction

The increasing demand for energy storage promotes the development of high-performance chemical power sources, and then promotes the research of secondary batteries with high energy density, long cycle life and portability[1][2,3]. At present, inorganic materials widely used in secondary batteries have some disadvantages, such as limited resources, serious environmental pollution and large energy consumption in production, which limit the development of secondary batteries[4]. Therefore, it is a new research direction to develop organic materials with abundant reserves in nature, low price, environmental friendliness and strong structural designability to replace inorganic materials[5,6].
covalent organic frameworks (covalent organic frameworks, COFs) are a new type of crystalline organic porous polymers, which are composed of carbon, hydrogen, oxygen, nitrogen, boron and other light atoms linked by covalent bonds to form a two-dimensional or three-dimensional topological network structure. The synthesis methods are gradually increasing through continuous exploration, mainly including solvothermal method, ionothermal method, microwave method, mechanochemical method and interfacial method[7][8][9][10][11][12]. Thanks to the reversible synthesis reaction controlled by thermodynamics, COFs have the functions of "error correction" and "self-repair", and then obtain thermodynamically stable target products[13]. The atoms are connected by covalent bonds to form a long-range ordered conjugated framework, and the layers can be stacked by non-covalent interactions to form a one-dimensional regular pore structure. This demonstrates the pre-design advantages of COFs materials. Therefore, COFs materials have a wide range of applications in catalysis, gas separation, medicine and other fields[14⇓⇓⇓~18].
In recent years, the application of COFs materials has been gradually extended to the field of secondary batteries[19,20]. multi-carbonyl COFs (Mc-COFs) are a kind of conjugated COFs with abundant carbonyl functional groups. Similar to metal-organic frameworks (MOFs), the introduction of carbonyl functional groups (C = O) into the framework can not only increase the polarity of the framework, but also maintain the structural stability of the material[21]. In addition, carbonyl groups can form radical anions by transferring reversible single electrons, and then combine with metal cations, which promotes the application of Mc-COFs in secondary batteries[22]. As shown in Figure 1, Mc-COFs are classified into neutral and ionic types according to the charged characteristics of the framework. Among them, neutral Mc-COFs can be used not only as electrode materials but also as solid electrolyte materials. As an electrode material, the carbonyl functional groups in the neutral Mc-COFs molecules undergo electron transfer during the charge-discharge process to realize the intercalation/deintercalation of metal ions; When it is used as a solid electrolyte material, carbonyl can promote the migration of metal ions in the battery[23]. However, ionic Mc-COFs are only suitable for solid electrolyte materials because their charged skeletons interact with the moving ions in the electrolyte, which can further enhance the ion migration rate[24]. In summary, by introducing as many carbonyl functional groups as possible into the conjugated framework of Mc-COFs, electrode materials with abundant active sites and solid-state electrolyte materials with excellent conductivity can be designed.
In this review, the applications of Mc-COFs in secondary batteries are summarized, the strategies for optimizing the electrochemical properties of Mc-COFs as electrodes are discussed, and the research progress in solid-state electrolytes is introduced.

2 Optimization of electrode materials for Mc-COF

Conjugated carbonyl compounds have shown great potential applications in the field of electrochemistry due to their advantages of fast reaction kinetics and high specific capacity[25]. When Huang et al. used calix [4] quinone as the cathode material for lithium ion batteries, the initial discharge capacity was 431 mAh·g-1 (theoretical capacity 446 mAh·g-1), but the discharge capacity decreased rapidly below 100 mAh·g-1 only after 5 cycles[26]. This is due to the fact that small conjugated carbonyl compounds are easily soluble in traditional organic electrolytes, resulting in rapid capacity decay[27]. Yao et al. synthesized PPTODB from pyrene-4,5,9,10 tetraone (PTO) and boroxane (planar boroxine,B3O3) and used it as a cathode material for lithium-ion batteries. After 150 cycles, the capacity retention rate of PPTODB was as high as 68.3%, and it also showed ultra-high rate performance and extremely stable coulombic efficiency[28]. In contrast, the use of Mc-COFs with ultra-large relative molecular mass and conjugated system in secondary batteries is beneficial to alleviate the dissolution problem of organic materials[29]. So far, the research of Mc-COFs materials in secondary batteries has been devoted to the improvement of specific capacity, cycle stability and rate performance, and the experimental results have achieved initial results, laying a solid foundation for the next practical application.

2.1 Increased active site

In general, the electrochemical energy storage of COFs electrode materials occurs at the redox active sites on the framework, and increasing the number of redox active sites in the COFs unit can significantly improve the theoretical capacity of COFs. Therefore, the capacity of COFs can be effectively improved by pre-designing the redox active sites to appear precisely at specific positions of the skeleton and show specific electrochemical properties.
Selecting building blocks rich in carbonyl groups is a direct way to increase the active sites of Mc-COFs. As shown in Figure 2, the common polycarbonyl building blocks are 1,3,5-triformylpholoroglucinol (Tp), pyromellitic dianhydride (PMDA), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) and hexaketocyclohexane (HKH)[12][30][31][32].
The imine group obtained from the condensation of the carbonyl group of Tp with the amine and the hydroxyl group of Tp can be converted into an irreversible enaminone structure, which enhances the stability of the skeleton structure and forms a C = O active site[33]. In order to increase the carbonyl active sites in electrode materials, Khayum et al. First synthesized Mc-COFs (HqTp) containing benzoquinone structure based on Tp and 2,5-diaminohydroquinone dihydrochloride (Hq) as building blocks and applied them to aqueous zinc batteries with a capacity of 276 mAh·g-1 at a current density of 125 mA·g-1[34]. Yang et al. broke through the limitation of accepting two electron-transferred quinone derivatives in the past and synthesized COF-TRO by reacting truxenone (TRO), which can undergo multi-electron redox reaction, with Tp. The all-solid-state lithium-ion battery assembled by COF-TRO as cathode material has a capacity of 268 mAh·g-1 at 0.1 C current density[35].
PMDA and NTCDA have high degree of conjugation and strong rigidity, and are difficult to deform. The loose carbonyl distribution on their frameworks is conducive to the intercalation/deintercalation of metal ions with larger radius, so that the carbonyl active sites can be fully utilized[36⇓~38]. The initial discharge capacity of Tb-DANT-COF synthesized from 1,3,5-triformylbenzene (Tb) and NTCDA was 144.4 mAh·g-1 at 0.34 C, which was very close to the theoretical capacity[39]. Although there are four carbonyl groups in PMDA and NTCDA molecules, in fact, in order to maintain structural stability, only the diagonal carbonyl groups react reversibly with metal ions, which results in the gap between material theory and actual capacity.
HKH, which is composed of only carbonyl groups, contains six carbonyl functional groups that can undergo redox reactions with metal ions, and has the highest theoretical capacity among the known multi-carbonyl compounds[40]. TQBQ-COF was synthesized by the Schiff-base reaction between the carbonyl group of HKH and the amino group of tetramino-benzoquinone (TABQ). In addition to the carbonyl group, the skeleton of TQBQ-COF also contains imine groups which can provide storage sites for metal ions[41]. Therefore, each unit of the TQBQ-COF material can provide 18 and 12 intercalation/deintercalation sites for Li+ and Na+, respectively, which can maximize the redox activity load while maintaining the conjugated structure of the molecule. As a result, the capacity of TQBQ-COF as the cathode material of lithium-ion batteries is as high as 502.4 mAh·g-1 in the second discharge, and the capacity is still 170.7 mAh·g-1[42] at 10 C high current density. The performance of TQBQ-COF in sodium-ion batteries is also excellent, with a high specific capacity of 452 mAh·g-1 and a capacity of 134.3 mAh·g-1 at a current density of 10 A·g-1[43].
In addition to the addition of carbonyl and imine groups as active sites, azo groups can also be added to the framework of Mc-COFs. Zhao et al. Synthesized Tp-Azo-COF by reacting Tp with 4,4 '-azodianiline (Azo), and used it as an anode material for lithium-ion batteries[44]. When discharging, the Li+ were intercalated into carbonyl and azo groups in sequence. In each unit, N = N and C = O could be combined with 12 and 18 Li+, respectively, and the initial discharge capacity was as high as 802.2 mAh·g-1. Since azo and imino groups were proved to be active sites to interact with metal ions, they have been increasingly designed into conjugated frameworks.
However, the method of increasing active sites to improve the capacity of electrode materials also has some limitations. At present, there are few functional groups that can be used as active sites, and researchers need to continue to develop functional groups that can participate in the reversible reaction of metal ions. When the conjugated skeleton contains two or more active sites, the electrochemical window of COFs is enlarged, resulting in more side reactions.

2.2 Improve the utilization rate of active sites

When Molina et al. used the anthraquinone-based redox-active conjugated microporous polymer (IEP-11-C) as a cathode material for lithium-ion batteries, the reversible capacity was only 40 mAh·g-1 (theoretical capacity was 149 mAh·g-1) at a current density of 1 C, and the material utilization was only 26%[45]. This phenomenon proves that only the active sites can fully react with metal ions to maximize the electrode capacity, so improving the utilization of active sites in Mc-COFs is one of the focuses to obtain high-performance electrode materials.
The active sites such as carbonyl, azo and imine groups are too close to each other, which leads to the large intramolecular steric hindrance, affecting the insertion/extraction of metal ions, thus inhibiting the utilization of active sites and making the actual capacity of the electrode lower than the theoretical capacity. However, when the material with loose active site distribution is used as the construction unit, the distribution density of redox sites can be effectively reduced, and the electrochemical performance of the electrode material can be improved. Tian et al. Synthesized polyimide (PI) -based conjugated microporous polymer PI-CMP by using NTCDA with loosely distributed carbonyl groups, Tb and hydrazine hydrate[46]. When PI-CMP was used as the cathode material for potassium-ion batteries, the initial charge and discharge capacity was 149, respectively, and the coulombic cycle efficiency reached 74% after 1000 cycles at a current density of 96.1%),1 A·g-1. It is worth noting that the construction of loosely distributed active sites will inevitably affect the theoretical capacity of electrode materials, so when designing Mc-COFs materials,A balance point should be found between increasing the number of active sites and reducing the distribution density of active sites, so that the electrode material can not only have an initial capacity infinitely close to the theoretical capacity, but also have a high retention rate after multiple cycles.
Bulk Mc-COFs are three-dimensional columnar structures formed by π-π interactions or intermolecular hydrogen bonds, which mask part of the active sites and hinder the diffusion of ions and the contact between metal ion pairs and active sites[47,48]. From the reported MOFs materials, it can be found that low-dimensional MOFs have better flexibility and abundant surface active centers than bulk MOFs[49⇓~51]. To this end, the nanosheet morphology can be obtained by destroying the π-π interaction between the layers of the bulk Mc-COFs, exposing the masked active sites[52,53]. When used as electrode materials, Mc-COFs with nanosheet morphology follows the surface ion storage mechanism, which maximizes the use of active sites while shortening the diffusion path of ions, and shows the actual capacity close to the theoretical value and super rate performance.
The methods for obtaining nano-thickness Mc-COFs fall into two categories. One is the physical method. For example, Wang et al. synthesized DAAQ-TFP-COF from 2,6-diamino-anthraquinone (DAAQ) and Tp, and mechanically polished it to obtain nano-thickness DAAQ-ECOF (Figure 3A)[54]. When DAAQ-ECOF was used as cathode material for lithium-ion batteries, the actual capacity reached the 145 mAh·g-1, which was 96% of the theoretical capacity. As shown in fig. 3 B, the DAAQ-ECOF has a reversible capacity exceeding the 107 mAh·g-1 at a high current density of 500 mA·g-1, reaching almost twice the capacity of DAAQ-TFP-COF. Another approach is to directly prepare the few-layer nanosheets by a chemical method[55]. Haldar et al. reported that IISERP-CON1 automatically shed into covalent organic nano sheets (CONs) during the growth of COFs[56]. IISERP-CON1 has an initial discharge capacity of up to 2060 mAh·g-1 at 100 mA·g-1 when used as an anode material for lithium-ion batteries.
The nanosheet form of Mc-COFs greatly improves the performance of the battery, but the two methods to obtain the sheet form of Mc-COFs also have shortcomings. It is difficult to accurately control the thickness of the nanosheets exfoliated by physical methods. There are unreacted raw materials and oligomers in the nanosheets synthesized by chemical methods, which lead to low synthesis yield and high difficulty in purification. This method usually requires the selection of a suitable substrate, and the difficulty in peeling the synthesized single-layer nanosheets from the substrate is also a problem that can not be ignored. In addition, compared with bulk Mc-COFs, the electrochemical stability of low-dimensional Mc-COFs is still worth exploring.

2.3 Improve electronic transmission capability

Introducing heteroatoms (such as N, O, S) that can reduce the energy gap of the framework and expanding the conjugated system of the framework with building units with a greater degree of conjugation are effective ways to enhance the electron and ion transfer ability of Mc-COFs, which is of great significance in improving the electrochemical performance of electrode capacity, cycle stability and rate capability[57][58]. Haldar et al. Synthesized Mc-COFs containing different numbers of nitrogen atoms (IISERP-COF16, IISERP-COF17, IISERP- COF18), in which IISERP -COF18 with the most nitrogen atoms has the narrowest energy gap[59]. The electrochemical performance of IISERP-COF18 was the best when they were used as anode materials for sodium-ion batteries. The specific capacity was 340 mAh·g-1 at 1 A·g-1 current density, and decreased by only 24% in the process of increasing from 0.1 A·g-1 to 1 A·g-1. Yang et al. compared the electrochemical performance of Tb-DANT-COF and Tp-DANT-COF with different conjugated degrees as cathode materials for lithium-ion batteries[39]. Although the theoretical discharge capacity of Tp-DANT-COF is higher than that of Tb-DANT-COF, the initial discharge capacity of Tb-DANT-COF(123.7 mAh·g-1) with higher conjugation degree is higher than that of Tp-DANT-COF(94.3 mAh·g-1) with lower conjugation degree at 1. 4 C, which indicates that increasing the conjugation degree of Mc-COFs skeleton can accelerate the electron conduction speed of the material.
In addition to the design of the framework of Mc-COFs, Mc-COFs can also be used to form composite materials with common conductive materials such as conductive polymers, carbon nanotubes (CNTs), graphene and so on[60]. Graphene is a two-dimensional honeycomb crystal composed of carbon atoms closely connected by benzene rings, which shows strong elasticity and super conductivity, and is often used as a conductive additive[61⇓~63]. Wang et al. compounded PI-ECOF-1 and PI-ECOF-2 with different qualities of reduced graphene oxide (rGO) by mechanical mixing method, and explored the effect of rGO content on the electrochemical performance of ECOFs in lithium-ion batteries[64]. The results showed that the electrochemical performance of the composite was the best when the mass fraction of rGO was 50%. At a high rate of 10 C, PI-ECOF-1/rGO50 still had a utilization of 67%, while the electrode without rGO showed almost no electrochemical activity. Compared with the mechanical mixing method, the distance between the COFs and the conductive material is shortened by the in-situ polymerization method, which is beneficial to the charge transfer between the COFs and the conductive material[65]. Luo et al. compounded poly (imide-benzoquinone) (PIBN) and graphene in this way to obtain PIBN-G. When PIBN-G and PIBN were used as the positive electrode of lithium ion battery, the reversible capacity was respectively the utilization rate of 271.0 mAh·g-1(96.8%) and the utilization rate of 244.8 mAh·g-1(86.1%), and the capacity was significantly improved after compounding[66]. In addition, the diffusion resistance and charge transfer resistance of PIBN-G are smaller (Figure 4A), which proves that the addition of graphene can increase the reaction kinetic speed of COFs and reduce its polarizability. The PIBN-G in fig. 4 B shows a smaller redox peak voltage difference, which also corresponds to the impedance results.
CNTs are conductive materials with zero-defect spatial topology, which are composed of one or more graphene sheets. The p orbitals of CNTs overlap with each other to form a highly delocalized large π bond, which makes it possible for CNTs to compound with two-dimensional conjugated polymers in a non-covalent manner. Xu et al. Synthesized DTP-ANDI-COF from NTCDA and 2,3,6,7,10,11-hexahydoxytriphenylene (HTTP) according to their previous work, and synthesized DTP-ANDI-COF @ CNTs by in-situ polymerization with CNTs[67][68]. When DTP-ANDI-COF @ CNTs was used as the cathode material for lithium-ion batteries, the coulombic efficiency was close to 100% after 700 cycles at a current density of 2. 4 C, and the capacity of the battery remained almost constant. based on the excellent cycling performance of DTP-ANDI-COF @ CNTs, Wang et al. used NTCDA and tris (4-aminophenyl) amine (TAPA) with better conductivity to synthesize 2D polyarylimide-based based covalent organic framework s (2D-PAI COFs) with a thickness of 4 ~ 6 nm, and used the same in-situ polymerization method for 2D-PAI COFs and CNTs to prepare composite 2D-PA1 @[69]. When the composite material is used as the anode material of the lithium ion battery, the composite material can be cycled for 8000 times under 0.5 A·g-1 current density, and the capacity is hardly attenuated. In lithium-sulfur batteries, the composite electrode materials formed by Mc-COFs and multi-walled carbon nanotubes (MWCNTs) have high structural rigidity, which can effectively inhibit the damage of the volume expansion of polysulfide intermediates to the structure of cathode materials. For example, Zhang et al. deposited a 25 nm TpPa-COF shell synthesized from Tp and p-phenylenediamine (Pa) on MWCNTs to obtain a novel core-shell TpPa-COF @ MWCNTs with a rigid network structure[70]. The composite has good stability and rate capability, and still has a high stable discharge capacity of 525.6 mAh·g-1 and an ultra-low capacity attenuation rate of 0.099% per cycle after 450 cycles. The composite also showed good electrochemical performance in lithium-selenium batteries, and the coulombic efficiency was 99% after 500 cycles at 3 C current density[71].
Mulzer et al. First introduced a conducting polymer poly (3,4-ethylenedioxythiophene) [PEDOT] into Mc-COFs containing anthraquinone building blocks by electropolymerization to obtain PEDOT @ DAAQ-TFP COFs[72]. It was found that the conductivity of the modified composites was greatly enhanced, and the composites could be applied to high-rate charging at 10 ~ 1 600 C. In order to further explore the effects of conducting polymers on the electrochemical performance of Mc-COFs with different transport modes, Vitaku et al. successfully designed and synthesized PEDOT @ DAAQ-TFP COF with reversible capacity affected by electron transport and PEDOT @ DAPH-TFP COF with reversible capacity affected by ion transport by electropolymerization (Fig. 6a), and used them as cathode materials for lithium-ion batteries, respectively[73]. When comparing the effect of PEDOT on conductive materials, it is found that the capacity of DAPH-TFP COF synthesized by Tp and 2,7-diaminophenazine (DAPH) is not changed, but the capacity of DAAQ-TFP COF is significantly improved, especially the cycle performance is greatly improved (Fig. 6B, C). The experimental results prove that the conductive polymer can optimize the electrochemical performance of Mc-COFs in the mode of electron transport.
It is difficult to achieve the uniform nano-size of the composite structure formed by the common mechanical mixing method, which makes the diffusion path of metal ions become tortuous. Excessive conductive materials will reduce the energy density of secondary batteries, limit the practical application of Mc-COFs as electrode materials, and thus hinder the improvement of electrochemical performance of secondary batteries.

3 Application of Mc-COFs in Solid Electrolytic

The tortuous and complex migration paths of ions limit the improvement of battery performance by a variety of solid-state electrolytes. In contrast, the regular pore structure of COFs materials can provide a single migration path for ions[74]. Vazquez-Molina et al. measured that the ionic conductivity of COF-5 particles was as high as 0.26 mS·cm-1 at room temperature, laying a foundation for the application of COFs materials in solid-state electrolytes for secondary batteries[75][76].
The lithium affinity of C = O and C = C on the framework of neutral Mc-COFs makes them uniformly distributed on the surface of metal lithium, forming a solid electrolyte membrane with uniform thickness. As a surface protective layer of metal lithium, the solid electrolyte membrane shows good physical and chemical stability, excellent structural designability and good barrier property[78][79][80][81]. The close contact between Mc-COFs and the lithium metal anode interface can effectively inhibit the formation of lithium metal dendrites and improve the safety of battery applications[82,83]. As shown in fig. 7A, Zhao et al. formed a novel artificial solid electrolyte interphase (ASEI) by in-situ embedding LiTFSI into a model compound (MC-TpPa) of a TpPa-COF membrane[77]. At room temperature, the lithium ion transference number in the novel ASEI is 0.79, and the ionic conductivity even reaches 0.53 mS·cm-1. The performance of ASEI was tested in Li | NCM battery, and the average coulombic efficiency was more than 99% after 150 cycles, which indicated that ASEI could inhibit the generation of side reactions and slow down the deposition of unstable metals. Although the metal protection behavior derived from the modification of Mc-COFs has broad prospects for development, this direction needs to be further studied.
Anion Mc-COFs can effectively avoid the free movement of anions by taking anions paired with metal ions as building units, so as to achieve the ideal state of only metal ion migration. The 3.44 Å in-plane spacing of lithium sulfonated COFs(lithium sulfonated COF,TpPa-SO3Li) allows the sulfonic acid group to be in close proximity to the carbonyl oxygen atom, and the Li+ to be able to move along the oxygen ion under cation-dipole interaction[84]. Thus, the ionic conductivity of TpPa-SO3Li is 2.7×10-2mS·cm-1, and the lithium ion transference number is as high as 0.9 at room temperature. When the TpPa-SO3Li was used as a solid electrolyte material in a Li ‖ Li symmetric battery, the plating/ionization of the Li+ was relatively stable during the 320 H cycle, and the surface of the lithium metal electrode was still smooth. When solid electrolyte interphase ASEI as the silicon anode of lithium-ion batteries, the solid electrolyte interphase (SEI) which can inhibit the natural growth on the surface of silicon nanoparticles can maintain a capacity retention rate of more than 60% after 1000 cycles at 2000 mA·g-1 and high current density[85]. In order to further improve the ionic conductivity of TpPa-SO3Li, Li et al. Proposed a pre-synthesis strategy with lithium salt as the building unit, and the conductivity of TpPa-SO3Li prepared by this method was improved to 1.6 mS·cm-1 at 0 ℃[86]. The pre-synthesis strategy is universal, and TpPa-SO3M(M=Li,Na,K) has been successfully synthesized, which expands its application in secondary batteries.
Cationic Mc-COFs can interact with the anions in the alkali metal salts to avoid the formation of ion pairs or ion aggregates between the metal ions and the anions in the alkali metal salts, thereby promoting the migration of the metal ions. Chen et al. combined the cation CON with the TFSI- in the lithium salt to form Li-CON-TFSI without adding any electrolyte to increase the free Li+ concentration (fig. 7B)[23]. The material has an ionic conductivity of 0.209 mS·cm-1 at 70 ° C. Due to the lack of ionic transport medium in ionic Mc-COFs, resulting in limited ionic transport capacity, Guo et al. Found that the EB-COF containing cationic framework prepared by ethidium bromide (EB) and Tp had excellent conductivity after polymerization with polyethylene glycol, which was 1.93×10-2mS·cm-1 at 30 ℃ and increased to 1.78 mS·cm-1 at 120 ℃[87].
Although the excellent thermodynamic stability and ionic conductivity of Mc-COFs make them perform well in the application of solid-state electrolytes, there are still the following problems: First, the protection mechanism of Mc-COFs as SEI for positive and negative electrodes still needs to be explored. Secondly, there are few kinds of Mc-COFs used as solid electrolyte materials. Based on the advantages of synthesizing Mc-COFs at the molecular level, new Mc-COFs can be designed according to the mechanism to expand the application scope of solid electrolyte. Thirdly, Mc-COFs can not show the best ionic conductivity at room temperature, and the ionic conductivity at room temperature can be improved by continuously optimizing the synthesis process.

4 Conclusion and prospect

In this paper, the recent applications of Mc-COFs in secondary batteries are summarized. As an electrode material, it shows excellent cycle stability, and its electrochemical performance can be further improved by the following methods. Firstly, carbonyl, imino, azo and other groups are introduced into the skeleton to increase the number of active sites and enhance the theoretical capacity. Secondly, in order to improve the utilization of active sites, the loose distribution of active sites on the framework was designed, and the nano-thickness of Mc-COFs was obtained by physical or chemical methods. Thirdly, in addition to introducing heteroatoms into the skeleton and expanding the degree of conjugation, Mc-COFs can also be compounded with conductive materials such as graphene, carbon nanotubes and conductive polymers to enhance their conductivity. When Mc-COFs are applied to solid electrolyte materials, polyethylene glycol (peg) is added to the pore structure to improve the ionic conductivity, in which ionic Mc-COFs promote the migration of target ions by developing charged building blocks.
Mc-COFs have made considerable progress in the application of secondary batteries, but it is still necessary to continue to explore the impact of structure on electrochemical performance to overcome the limitations of Mc-COFs in secondary batteries. Continuously enrich the means of mechanism exploration to fully understand the reaction mechanism of electrodes and solid electrolytes. At present, the sequence of metal ions intercalated into the active sites and the utilization degree of the active sites in the conjugated skeleton have not yet formed a system. In addition, due to the harsh synthesis conditions and high preparation cost of Mc-COFs, it is difficult to achieve large-scale use, so it is necessary to develop a simple and efficient synthesis method to accelerate its development in secondary batteries. It is believed that there will be more and more high-performance Mc-COFs secondary batteries with the deepening of the research on Mc-COFs.

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Funding

National Natural Science Foundation of China(21875206)

National Natural Science Foundation of China(21403187)

Natural Science Foundation of Hebei Province(B2019203487)

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