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Application of Metal-Organic Framework Materials in the Field of Energy Storage

Hanlin Shen , Min Dai , Zhuo Li , Yunan Tian , Tianwei Li , Xianwei Hu

Progress in Chemistry ›› 2024, Vol. 36 ›› Issue (5) : 724 -740.

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Progress in Chemistry ›› 2024, Vol. 36 ›› Issue (5) : 724-740 DOI: 10.7536/PC230823
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Application of Metal-Organic Framework Materials in the Field of Energy Storage
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Abstract

Due to the characteristics of large specific surface area,porosity,adjustable structure and easy modification,metal-organic framework materials and their derivatives are widely used as electrode materials,separators,electrocatalysts and other energy storage materials.However,there are still many problems In the practical application of MOFs.This paper reviews the latest developments in the application of MOFs and their derived materials in energy storage devices such as alkali metal ion batteries,metal chalcogenide batteries,aqueous zinc ion batteries,and supercapacitors,and proposes design solutions for problems such as dendrite growth and shuttle effects that often occur in secondary batteries.in addition,the design ideas of MOFs-derived carbon material heterostructure and metal compound structure modification are also summarized.Finally,the intrinsic regulation of MOFs precursors and the modification strategies of derived materials are summarized and prospected。

Contents

1 Introduction

2 MOFs are used in the field of energy storage

2.1 Applications in lithium-ion batteries

2.2 Applications in sodium-ion batteries

2.3 Applications in potassium-ion batteries

2.4 Applications in metal-chalcogen batteries

2.5 Applications in aqueous zinc-ion batteries

2.6 Applications in supercapacitors

3 Modification strategies for MOFs and their derived materials

3.1 Intrinsic regulation of MOFs

3.2 MOFs-derived carbon materials

3.3 MOFs-derived metal compounds

4 Conclusion and outlook

Graphical abstract

Keywords

metal-organic framework materials / secondary battery / MOFs derived materials / modification strategy

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Hanlin Shen, Min Dai, Zhuo Li, Yunan Tian, Tianwei Li, Xianwei Hu. Application of Metal-Organic Framework Materials in the Field of Energy Storage. Progress in Chemistry, 2024, 36(5): 724-740 DOI:10.7536/PC230823

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1 Introduction

With the over-exploitation of oil resources and the excessive use of fossil fuels,a large number of carbon dioxide emissions have been caused,which makes the environmental pollution problem more and more serious[1]。 in order to solve environmental problems,renewable energy,especially in the field of electrochemical energy storage,has attracted wide attention of researchers in recent years[2,3]。 For energy storage devices,while being safe and environmentally friendly,the improvement of energy density,cycle life and fast charge-discharge ability is also very important.Therefore,it is urgent to develop a material with high theoretical capacity to meet the demand of high specific energy battery capacity。
Metal-organic frameworks(MOFs),also known as porous coordination polymers(PCPs),are coordination polymers(o-CPs)bridged by organic ligands and metals[4]。 Generally,MOFs materials are crystalline materials made of metal nodes and Organic ligands,and their metal nodes can be ions of alkali metals,transition metals,or lanthanides.organic ligands are usually based on N-donor groups,carboxylates,phosphates,etc[5]。 This kind of material has completely regular morphology,high porosity and controllable structure,and has broad application prospects in gas storage,catalysis,chemical sensing and other fields[6][7]。 the research on MOFs materials can be traced back to the MOF-5 and subsequent zeolite-like imidazole framework(ZIF)series proposed by Yaghi et al.,and their permanent porosity and high thermal stability have been verified,laying a solid foundation for the preparation and application of MOFs derived materials[8][9]。 In the subsequent research of metal-organic framework materials,different types of MOFs used in various fields have been developed according to different metal nodes or organic ligands,including IRMOF(mostly used for gas selective capture),ZIF(commonly ZIF-8,ZIF-9,ZIF67,etc.),MIL(mostly composed of high-valence metal cations such as Fe3+,V3+,Al3+and organic ligands such as BTC or BDC),PCN,UIO,etc[10][11]。 Solvothermal method,electrochemical method,direct precipitation method,microwave-assisted method,mechanochemical method,ultrasound-assisted method and self-assembly method are commonly used in the synthesis of MOFs[12]。 In 2017,Rubio-Martinez et al.Reviewed the synthesis schemes of MOFs from laboratory to industrialization,and considered that solvent-free method and aqueous phase synthesis method were the most likely strategies for large-scale production[13]。 At the same time,in recent years,various series of primitive MOFs and their derived materials have also received extensive attention in the field of energy storage,and finding suitable preparation methods and performance control strategies is the key direction of MOFs and their derived materials research。
in recent years,researchers have carried out a lot of research on the application of MOFs materials in the field of energy storage.Liang et al reviewed the application progress of MOFs materials in lithium-ion batteries,lithium-sulfur batteries,lithium-oxygen batteries and supercapacitors,but did not involve the application of other alkali metal ion batteries[14]。 Wang et al.Made a comprehensive summary of the application of MOFs and their composites,but there is still a lack of effective guidance for the structural design of MOFs[15]。 in this paper,the application of MOFs in secondary batteries and supercapacitors is comprehensively summarized,and the structural design and modification strategies of MOFs derived materials are discussed.It is hoped that this review will help readers to have a more comprehensive understanding of the application of MOFs in the field of energy storage and design MOFs materials with better electrochemical performance。

2 Application of MOFs in energy storage

Secondary battery is one of the important devices for sustainable energy development,which has the advantages of environmental friendliness,low cost,high energy density and good cycle performance.It mainly includes alkali metal ion batteries(lithium ion,sodium ion,potassium ion batteries),metal-chalcogenide batteries,aqueous zinc ion batteries,air batteries,supercapacitors(SCs)and so on[16][17][18][19][20]。 However,the energy density has still not reached a high level in the currently studied secondary battery systems,in which electrode materials play an important role in improving battery performance.At present,most of the electrode materials commonly used in alkali metal ion batteries have low theoretical capacity,which seriously limits their further development;the commercialization of lithium-sulfur batteries is also plagued by the shuttle effect and the slow kinetic transformation of polysulfides,which makes the research and preparation of high-performance electrode materials for secondary batteries more and more important[21]。 the high porosity of MOFs ensures the uniform distribution of internal active sites,and the open structure of the framework enables the transformation into a multi-level structure after synthesis treatment,which is conducive to the continuous electrochemical reaction[22]。 the original MOFs materials have weak conductivity and poor electrochemical stability,so MOFs materials can be used as precursors to prepare MOFs derivative materials,thus effectively improving The battery performance。

2.1 Application in lithium-ion batteries

Lithium-ion batteries(LIBs),as the most widely studied energy storage system in the secondary battery system,have a higher working voltage,which is three times that of nickel-hydrogen batteries,usually greater than 3.6 V,and a higher power density.It has been widely used in the market of power batteries,energy storage batteries and portable electronic devices[23]。 In recent years,the theoretical capacity and specific energy density of traditional lithium-ion batteries with lithium cobalt oxide and lithium iron phosphate as the cathode and graphite as the anode have reached the upper limit,which hinders the further development of lithium-ion batteries.Therefore,researchers have tried to improve the capacity and rate performance of lithium-ion batteries by preparing MOFs-related materials instead of traditional electrode materials。
the porous structure of MOFs can enhance the contact area between the active material and the electrolyte,which is conducive to the improvement of the rate performance of lithium-ion batteries and the rapid diffusion of lithium ions,so it shows great potential as an electrode material for lithium-ion batteries[12]。 Lin et al.Used a solvothermal method to synthesize a Cd-MOF with excellent thermal stability and further calcined it at 800°C under nitrogen protection to obtain a nitrogen-doped carbon material NC800,which was tested to have excellent cycling stability(after 100 cycles at a current density of 100 mA·g-1,the specific capacity remained at 741 mAh·g-1）[24]。 Recently,the multi-metal doping modification of MOFs has been widely studied as anode materials for lithium-ion batteries.The construction of bimetallic MOFs can enhance their electrochemical performance,because the multi-component metal nodes can expose more reactive sites,and the obvious advantages of kinetics and thermodynamics can constitute a synergistic effect.Yan et al.Constructed a bimetallic Co4(μ4-O)[Ir(ppy-COO)3]2MOF（Co4-Ir MOF）as an anode material for lithium-ion batteries.Such bimetallic MOFs composed of Ir(ppy-COOH)3bridging-coordinated Co4(μ4-O)clusters(Figure 1A)have 4 orders of magnitude higher electrical conductivity and 2 orders of magnitude higher Li-ion diffusion coefficient than conventional insulating MOFs,reaching a good rate capability of 515 mAh·g-1at 3000 mA·g-1[25][26]。 Multi-metal materials are used as precursors to further prepare metal selenides.The higher polarization of selenium can theoretically bring better rate performance,while nitrogen-doped carbon can improve conductivity.Zhang et al.Proposed a KOH-assisted aqueous strategy to synthesize a series of bimetallic MOFs materials,which were further carbonized and selenized to obtain 3D polyhedral Fe-Co-Se/NC with intact porous structure.As a lithium-ion anode,the initial discharge specific capacity was up to 1165.9 mAh·g-1at a current density of 1.0 A·g-1,and the reversible capacity was 1247.4 mAh·g-1（after 550 cycles(Fig.1D )[27]。
Recently,Dai et al.Synthesized bimetallic MOFs material TCPP(Fe)-Ni by solvothermal method,which showed excellent rate performance and high reversible capacity of 950 mAh·g-1at 0.1 A·g-1when used as anode material for lithium-ion batteries[28]。 Yin et al.Proposed a simple one-step method to synthesize two-dimensional c-MOF Cu3(HHTP)(THQ)based on two ligands,in which ethylenediamine was used to balance the competitive coordination between HHTP and THQ ligands,which opened up a new way for the synthesis of two-dimensional c-MOF with two ligands[29]。
MOFs and their derivatives are considered to be excellent candidates for electrode materials for lithium-ion batteries.In order to effectively improve the electrochemical performance,the strategies of doping multi-metal components and preparing metal matrix composites are proposed,which help us further explore the application of MOFs derivatives as anode materials for lithium-ion batteries。

2.2 Application in sodium-ion battery

sodium is abundant in natural resources and cheaper,and its electrochemical mechanism is similar to that of lithium-ion batteries,so it is expected to replace lithium-ion batteries in large-scale energy storage applications.However,sodium has a larger ionic radius than lithium(102 pm vs.76 pm),resulting in slow kinetics of the electrode material during sodium intercalation/deintercalation cycles and large structural changes in the matrix material.Therefore,electrode materials with good structural stability should be developed to achieve improved electrochemical performance of sodium-ion batteries(SIBs)[30]。
in order to improve the sodium storage performance,carbon materials(including graphite,amorphous carbon,heteroatom-doped carbon and biomass-derived carbon)have been widely studied In recent years.Based on this idea,carbon materials derived from MOFs may become high-performance anode materials for sodium-ion batteries because they not only retain the original high pore structure but also enhance the conductivity[31]。 Cui et al.Proposed that heteroatom doping in porous carbon materials improves the sodium storage performance[32]。 Based on the concept of excellent sodium storage for heteroatom-doped carbon materials and metal phosphides,recently,Zhao et al.Mixed ZIF-67 and red phosphorus,and further calcined in a protective atmosphere to obtain nitrogen-doped cobalt phosphide carbon composite Co2P@NC-12.5（Fig.2a),which showed a reversible capacity of more than 350 mAh·g-1at a current density of 0.1 A·g-1when used as an anode material for sodium-ion batteries[33]。 Feng et al.Prepared the CoSe@NC/MoSe2bimetallic selenide composite(Figure 2D)by combining the ideas of metal selenide,nitrogen doping,and carbon skeleton to prepare the composite[34]。 This multi-component composite strategy improves the sodium storage performance,while the nitrogen-doped carbon matrix ensures the sodium ion transport capacity.After 1500 cycles at a current density of 5.0 A·g-1as a sodium ion anode material,the discharge capacity was 305.9 mAh·g-1（Fig.2 e).Li et al.Grown a new carbon allotrope,graphite-like crystal,under sufficient graphite induction conditions,and successfully prepared Zn-TDPAT MOF-derived crystalline carbon by controlling the reaction inflection point temperature under graphite induction(Fig.2F).The Zn-TDPAT-GC electrode showed excellent electrochemical performance and good structural stability when applied to sodium ion anode.The reversible capacity was 354 mAh·g-1after 50 cycles at a current density of 20 mA·g-1,which was 97.5%of the initial capacity,and 293 mAh·g-1after 100 cycles at a current density of 100 mA·g-1,which was 90%of the initial capacity(Fig.2 H )[35]。
Recently,the ideas of defect introduction and heteroatom doping have been widely used in the research of improving the performance of electrode materials for sodium-ion batteries.Yao et al.Doped in MIL-125 by solvothermal method,and then further prepared Si-TiO2-x@C materials with Si atom doping and oxygen vacancy defects by annealing and NaOH etching.The existence of oxygen vacancy defects was verified by EPR,which enhanced the conductivity and reaction kinetics.When the Si-TiO2-x@C materials were used as sodium ion anode materials,they showed excellent performance[36]。 Feng et al.Prepared MIL-101(Al)-NH2MOF as a precursor,and then mixed with sulfur and calcined to obtain a nitrogen/sulfur binary doped microporous carbon material NSPC as an anode material for sodium-ion batteries.The initial coulombic efficiency(ICE)was improved due to the coating effect of sulfur in the micropores,which reduced the internal defects of the micropores[37]。 the adsorption energy of sodium ions on the surface of nitrogen/sulfur co-doped carbon materials was significantly increased(-0.5 eV to-2.07 eV)compared with that of nitrogen doped carbon materials,which proved that the synergistic effect of double heteroatom doping increased the diffusion rate of sodium ions。
MOFs-derived carbon materials,Metal compounds And multi-component doped composites combine their respective advantages and show excellent electrochemical performance in sodium-ion batteries.metal compounds improve the performance of sodium storage,and heteroatom doping(Si,N,S,etc.)and defect regulation effectively enhance the reaction kinetics.These modification design strategies contribute to the rapid development of MOFs as anode materials for sodium-ion batteries。

2.3 Application in potassium ion battery

potassium resources on the earth are more abundant than lithium resources,and the conductivity of Potassium electrolyte is better,and the voltage platform and energy density are higher[38]。 the similar working mechanism of lithium-ion batteries makes potassium-ion batteries(PIBs)promising as one of the alternatives to lithium-ion batteries.the radius of potassium ion(138 pm)is larger than that of lithium ion and sodium ion,which leads to the fact that many electrode materials suitable for lithium ion batteries can not be directly applied to potassium ion batteries.It will lead to huge volume expansion and serious capacity fading in the process of potassium intercalation/deintercalation,so finding anode materials that can reversibly accommodate potassium ions is the key to promote the development of potassium-ion batteries[39]。
In order to solve the problems of low capacity and poor cycle performance of electrode materials,Xiao et al.Grew Co-MOF nanocrystals uniformly anchored on graphene oxide through the synergistic coordination and electrostatic interaction between GO and Co-MOF,and further annealed to obtain a hybrid material composed of Co-MOF nanocrystals tightly coated with reduced graphene oxide(rGO)network(Figure 3A)[40]。 When the prepared three-dimensional graphene-network-encapsulated Co-MOF nanocrystals(Co-MOF-rGO)was used as the PIB anode material,it showed a reversible specific capacity of 422 mAh·g-1at 0.1 A·g-1,and the discharge specific capacity could still reach 202 mAh·g-1even at a large current density of 5 A·g-1,demonstrating the excellent rate capability of Co-MOF-rGO,with a decay rate of only 0.013%per cycle after 2000 cycles at 2 A g-1(Fig.3 B).In recent years,bismuth-based MOFs have been widely used as anode materials for potassium-ion batteries.Bismuth is non-toxic and environmentally friendly,with a theoretical mass specific capacity of（386 mAh·g-1）and a high volume specific capacity(3800 mAh·L-1）.The coordination of Bi metal center with potassium ion can increase the reversible ability,but there are also problems of volume expansion(PIBs about 411%)and electrode pulverization inherent to bismuth metal as a negative electrode[41]。 Based on this idea,Sun et al.Synthesized a novel flower-like Bi-MOF assembled by two-dimensional porous nanosheets by solvothermal method,and further calcined Bi@N-CNCs with melamine as nitrogen source in Ar atmosphere(Fig.3C).When the further optimized 850Bi@N-CNCs were used as anode materials for potassium-ion batteries,the reversible capacities were 334.3 and 221.3 mAh·g-1at a current density of 0.5 and 10.0 A·g-1,respectively,and the capacity fading rate was only 0.004%per cycle after 1200 cycles at 5.0 A·g-1[42]。 Recently,Li et al.prepared a 3D-structured Bi-MOF(Figure 3D)as a potassium ion anode material through metal bismuth and terephthalic acid.the three-dimensional porous structure of the nanoscale pore disperses the stress generated by the alloy reaction,effectively suppresses the volume expansion problem,and thus promotes the ion transport capability[39]。 When used as an anode material for PIB,the Bi-MOF delivered a high reversible capacity of 415 mAh·g-1after 500 cycles at 0.1 A·g-1and excellent cycling stability(315 mAh·g-1）at 0.5 A·g-1at 1200 cycles.Selenides have also been used in combination with porous carbon materials for potassium storage applications.Chen et al.Synthesized Bi-MOF by hydrothermal method,and after further pyrolytic selenization under Ar atmosphere,synthesized Bi/Bi3Se4@CNR composite composed of rod-like porous carbon skeleton in the outer layer and Bi/Bi3Se4nanoparticles in the inner layer(Fig.3e),and in situ characterization proved that the potassiation/depotassiation process was controlled by the dual mechanisms of conversion and alloying/dealloying reactions[43]。 The battery can exhibit a good reversible capacity of 307.5 mAh·g-1at 20 A·g-1.After 2000 cycles at 5 A·g-1,the capacity reached 254.8 mAh·g-1.In addition,Bi/Bi3Se4@CNR/KVO full batteries also show some application potential 。
MOFs composites prepared by adding carbon-based materials such as graphene and graphene oxide have effectively improved the electrochemical performance of anode materials for potassium-ion batteries,and two-dimensional and three-dimensional structures and metal selenides have also shown great potential in anode materials for potassium-ion batteries in recent years。

2.4 Application in alkali metal-chalcogenide batteries

the negative electrode of the battery is made of alkali metal,and the positive electrode is made of chalcogenide.This kind of alkali-chalcogenide battery has become a hot topic in the field of energy storage batteries because of its low cost,large theoretical capacity,green environmental protection and other characteristics[17]。 For example,lithium-sulfur batteries include a lithium metal negative electrode,an organic electrolyte,and a sulfur composite positive electrode.In the research of this kind of battery,MOFs materials can be used as active materials to suppress the volume expansion of the electrode during charge and discharge.the modified separator and protective coating prepared by MOFs can also solve the shuttle effect caused by the intermediate entering the electrolyte and the dendrite growth caused by the alkali metal electrode。
in order to effectively limit the shuttle effect of polysulfides(long-chain polychalcogenides produced by the positive electrode of alkali-metal chalcogenide batteries can dissolve in common ether electrolytes and react with the negative electrode through the separator,resulting in irreversible losses),Zheng et al.It is found that the interaction between Lewis acidic Ni(II)centers and Lewis basicity of polysulfides can successfully capture polysulfides in the framework of MOFs and enhance their cycle stability.This confirmation of polysulfide absorption based on Lewis acid-base theory helps to improve the design of such battery materials[44][45]。 Bai et al.Designed and prepared a microporous MOF@GO separator for lithium-sulfur batteries(Figure 4A),which has regular pores of about 99Å,effectively blocking the passage of polysulfides and allowing the normal movement of lithium ions[46]。 Based on the previous idea of MOFs separator preparation,Li et al.Recently developed a functional separator for lithium-sulfur battery ZIF-67 in-situ growth of sodium alginate fiber membrane by electrospinning(Fig.4B).As a new multifunctional lithium-sulfur battery separator(ZIF-67/SA-PAN),the SA fiber membrane prepared by in-situ loading ZIF-67 on polyacrylonitrile(PAN)matrix can effectively isolate polysulfides(Figure 4C),and shows good rate performance and cycle stability in further tests[47]。 Geng et Al.Prepared MIL-96-Al with different shapes and sizes,and analyzed the effects of shape and size on its electrochemical performance,which provided an improvement idea for the size design of MOFs materials[48]。
in the aspect of limiting the dendrite growth of alkali metal anode in lithium-sulfur battery,Song et al.Prepared Bio-MOF-100,and then carbonized it at 800℃for 8 H in Ar atmosphere to obtain amorphous carbon material ZnENC[49]。 SAZ-AF Janus membrane was prepared by coating Bio-MOF-100 and ZnENC on both sides of Celgard membrane.The Bio-MOF-100 coating layer toward the lithium anode side separator effectively induced uniform and fast transport of lithium ions(Figure 4D),which can suppress dendrite growth even at high current densities.The introduction of additional metal nodes into MOFs materials can effectively optimize the application of MOFs materials in lithium-sulfur batteries.This is due to the fact that MOFs materials with bimetallic and multimetallic nodes can enhance the absorption of polysulfides in lithium-sulfur batteries.Recently,Zhu et al.Proposed to encapsulate Ni-Co bimetallic phosphide into a nitrogen-doped double carbon conductive network(NiCoP@NC)by high temperature annealing and phosphating Ni-ZIF-67 precursor(Fig.4E),and the encapsulated Ni/Co phosphide particles can significantly enhance the catalytic conversion of lithium polysulfides.As a modified separator for lithium-sulfur batteries,it helps lithium-sulfur batteries to exhibit good specific capacity(the initial capacity at 0.5 C is 1083.4 mAh·g-1）)and good cycle stability(the capacity fading rate is only 0.09%at 300 cycles )[50]。 For the synthesis of multi-metal doping,the one-pot synthesis method can be used,and the ion exchange method can also be used by soaking the monometallic MOFs in different concentrations of metal ion solution[51]。 Li et al.Prepared a series of Mn-based multimetallic MOFs(bimetallic and trimetallic MIL-100)nanooctahedra(Figure 4 f)through a one-pot synthesis strategy,which were used as sulfur carriers for lithium-sulfur battery cathodes,and the MnNiMIL-100@S cathode showed the best lithium-sulfur battery performance after testing,with a reversible capacity of about 708.8 mAh·g-1after 200 cycles[52]。
Modified separators based on MOFs and their derivatives can effectively adsorb polysulfides when applied to metal-chalcogenide batteries.A separation membrane(Janus separator)with an asymmetric structure can be prepare as a coating layer to induce uniform deposition of a lithium anode to a certain extent.In addition,the cathode sulfur support materials prepared by multimetallic MOFs also show good electrochemical performance。

2.5 Application in aqueous zinc-ion battery

Compared with non-aqueous system,aqueous zinc-ion battery has higher safety and lower cost,so it has been widely concerned by researchers.Manganese-based and vanadium-based oxides,Prussian blue analogues,and metal salts of the Prussian blue type have been studied as cathode materials for aqueous zinc-ion batteries[53]。 However,due to the low specific capacity of cathode materials and the dendritic growth of anode zinc metal(caused by uneven zinc deposition),the further development of aqueous zinc-ion batteries is still seriously hindered[54]。 In order to improve the above problems of aqueous zinc-ion batteries(ARZIBs,ZMB),researchers have done a lot of work on the application of MOFs materials as cathode materials,anode materials,separators and solid electrolytes[18]。
In terms of alleviating the dendrite growth of zinc anode,MOFs materials are often used to prepare ion sieves due to their structural characteristics,but the prepared ion sieves are still vulnerable to severe polarization and dendrite growth after multiple cycles on ZMB[55]。 Lei et al.Experimentally demonstrated that two-dimensional MOFs nanosheets(Figure 5A)can act as a protective coating to inhibit dendrite formation[56]。 In addition,the researchers compared the differences between UiO-67-3D and UiO-67-2D materials as zinc anode coatings,and verified that the two-dimensional structure has a higher concentration of Zr-OH/H2O zincphilic sites,which can induce the uniform deposition of Zn and better inhibit the growth of zinc dendrites.The UiO-67-2D@Zn||Mn2O3/C battery tested by this coating also achieved good reversible capacity,rate performance and cycle stability.Yang et al.Proposed to use MOFs coating on Zn surface for high-performance MnO2-Zn batteries,and the construction of MOFs coating layer to obtain uniform Zn deposition and then prevent the dendrite growth of zinc anode(Fig.5B )[57]。 The symmetrical Zn half cell was maintained for a lifetime of up to 3000 H at a current density of 0.5 mA·cm-2.When complexed with MnO2cathode,the reversible capacity was 180.3 mAh·g-1with a capacity retention of 88.9%after 600 cycles at a MnO2loading up to 4.2 mg·cm-2.Similarly,UiO series MOFs were designed to solve the problem of zinc anode dendrite growth.Xu et al.Prepared a UiO-66 defect layer(Figure 5C),and further prepared a defect MOF(D-UiO-66)on the zinc surface,and then used the quasi-solid interface phase composed of it and two zinc salt electrolytes as the zinc ion reservoir[58]。 By verifying the anion adsorption and zinc ion transfer efficiency of Lewis acid sites in the defect layer of MOFs,the concentration of zinc ions near the anode is increased,which further proves that it can inhibit the dendrite growth of zinc。
Because the regulation of intrinsic structure is an effective modification strategy to enhance electrochemical performance,researchers found that the steric hindrance of lattice space can hinder the efficiency of zinc ion transport.To this end,Ren et al.Used amorphous metal-organic framework materials(aMOFs)synthesized by Zr4+and ATMP one-step solvothermal method to prepare artificial SEI films,which achieved better zinc ion transport and uniform deposition according to their defects and dangling bonds and microporous structure different from crystalline MOFs,which also opened the way for aMOFs to be applied to aqueous zinc-ion batteries[59]。 In addition,Yin et al.Made cathode materials through the idea of coordination unsaturation,in which three Mn-based MOFs with different coordination degrees were synthesized by adjusting the molar ratio of Mn to H3BTC during the preparation process(Fig.5d)(in which the molar ratio of Mn to-COOH was 1:Subsequent tests verified that Mn-H3BTC-MOF-4 at a molar ratio of 1:4 possessed a better zinc ion storage capacity than several other coordination degrees(excellent capacity of 138 mAh·g-1at 100 mA·g-1and 93.5%capacity retention after 1500 cycles at 3000 mA·g-1)(Fig.5e )[60]。 Recently,based on 2D-MOF materials,Wang et al.Proposed an alternative stacked Cu-HHTP/MX heterostructure prepared by solution phase direct assembly strategy for aqueous zinc-ion battery cathode materials(Figure 5F),which was tested to have a capacity of 260.1 mAh·g-1at a current density of 0.1 A·g-1,a rate capability of 173.1 mAh·g-1at a current density of 4 A·g-1,and a capacity retention of 92.5%after 1000 cycles[61]。
the strategy of using MOFs to prepare coatings has effectively alleviated the problem of zinc anode dendrite growth in aqueous zinc-ion batteries,and the intrinsic structural regulation of MOFs materials also provides a new idea for enhancing the storage and transport capacity of zinc ions。

2.6 Application in Supercapacitor

supercapacitors(SCs)consist of a positive electrode,a negative electrode,an electrolyte,and a separator.According to the energy storage mechanism,Supercapacitors can be generally divided into electric double layer capacitors(EDLCs)and pseudocapacitors(Faraday pseudocapacitors)[62,63]。 For the application of MOFs in SCs,their large specific surface area can enlarge the contact area between the electrolyte and the MOFs electrode,thereby improving the specific capacitance.the adjustable pore size can ensure the rapid transport of electrolyte ions and electrons,and the abundant active sites can improve the pseudocapacitance[5]。
Sheberla et al.Proposed the use of pure Ni3(HITP)2as an active material for EDLCs(Figure 6A),based on the good electrochemical performance of Ni3(HITP)2materials,making it the first precedent for pure MOFs materials to be used as electrodes for electric double layer capacitors[64]。 Liang et al.Mentioned the development strategy of its application in supercapacitor electrode materials in their review on the application of basic MOFs and composite MOFs[14]。 Most of the basic MOFs are prone to collapse in both acidic and alkaline application environments,so a series of ideas are proposed:(1)the introduction of multi-metals into MOF-74 series helps to improve the redox behavior in cyclic voltammetry and galvanostatic charge-discharge curves;(2)sp2hybridized nitrogen atoms in the ligand can increase the interaction with ions in UiO-based MOFs;(3)nMOF-867 is a suitable sample for both particle and pore size of synthetic nMOF.In addition,in the research of MOFs composites,high conductive materials(such as graphene,GO,rGO,CNTs and conductive polymers)are compounded with the original MOFs to further synthesize MOFs composites,which can improve the conductivity of the original MOFs and accelerate the research of SCs electrode materials[65]。 In a recent study,Fan et al.introduced Co into MOF-74 and anchored and dispersed Co-MOF-74 nanoparticles on 3D functionalized graphene oxide(FGO)(Fig.6B),and applied it as a negative electrode material in a sodium-ion hybrid capacitor(SIHC).The prepared Co-MOF74|FGO-180 electrode has a high specific capacity of 1170 mAh·g-1at a current density of 0.1 A·g-1.The reversible capacity after 100 cycles at a current density of 0.1 A·g-1was about 416 mAh·g-1,and the Co-MOF-74|FGO180//AC device exhibited excellent performance(the maximum energy density and power density were 240 Wh·kg-1and 10 kW·kg-1,and the cycling stability was excellent)(Figure 6C )[66]。
Based on the above summary,when MOFs materials are used as electrode materials for alkali metal ion batteries,the electrochemical performance can be effectively improved by regulating the multi-metal synergistic effect,doping of heteroatoms,composite graphene oxide and other strategies.the modified separator made of MOFs materials can be applied to lithium-sulfur batteries to control the shuttle effect of polysulfides;Secondly,MOFs materials can also be used to prepare protective coatings to solve the problems of dendritic growth of anodes in aqueous zinc-ion batteries;MOFs or their composites can be used to prepare electrode materials with high electrochemical performance in supercapacitors.A variety of post-treated materials(doped carbon materials,MOFs/rGO composites,etc.)have been proved to be effective in improving the electrochemical performance of energy storage devices.in addition,some unsaturated coordination States are regulated,and the introduction of amorphous MOFs is also gradually applied in the field of energy storage。

3 Modification Strategies of MOFs and Derivative Materials

3.1 Intrinsic Regulation of MOFs

The MOFs obtained by selecting appropriate metal ions and organic ligands for coordination can be directly used in the field of energy storage.In the early research on the application of MOFs materials in lithium storage,Li et al.,inspired by the application of MOF-177 in hydrogen storage,explored its use as an electrode material for lithium storage.They synthesized MOF-177 by solvothermal synthesis and tested it as an anode active material.As a result,the capacity fading rate is very high(the capacity in the first cycle is more than 400 mAh·g-1,and the capacity in the second discharge process is only 105 mAh·g-1）.This study opens the way for the subsequent application of MOFs materials in lithium-ion battery electrode materials[67]。 Since then,MOFs have been widely used in electrode materials research.Maiti et al.Prepared Mn-BTC by solvothermal method and applied it to the anode of lithium-ion battery,and the specific capacity reached 694 mAh·g-1at the current density of 0.1 A·g-1[68]。 MOFs with different morphologies,such as microporous Pb-MOF with three-dimensional framework and one-dimensional rhombic channels for lithium-ion anode(Fig.7A),have been obtained by matching various metals with suitable organic ligands.Ti-MOF with stable skeleton and hexagonal nut shape for lithium-ion battery anode(Figure 7 B),cubic cage-like manganese-based MOF(Mn-CCs)(Figure 7 C)are used for lithium-sulfur battery cathode to capture original MOFs such as polysulfides[69][70][71]。
the properties of MIL series in pristine MOFs have also been extensively studied,and Millange et al.Proposed The first MIL series skeleton:MIL-53 as early as 2002[72]。 When the MIL series is subsequently applied to energy storage devices,it is found that the pore size and structure of the MIL series need to be regulated by selecting appropriate metal salts and organic ligands,so as to provide a variety of MIL structures,such as rods,spindles,etc.These structures are helpful to retain the original structure when the MIL series is calcined and carbonized as a precursor,or to improve the conductivity and charge storage ability as a basic template for modified materials.For example,Zhu et al.Synthesized disk-shaped MIL-125(Ti)derivative Li4−xKxTi5O12for lithium-ion battery anode,and Zhao et al.Synthesized micron-sized materials based on MIL-88a modified by polyoxometalate for lithium-ion battery anode.Ma et al.First proposed that TB-FeOSC-NS was prepared by calcination under certain conditions using MIL-88 B(Fe)as a self-sacrificial template,and the optimized sheet-like heterostructure enhanced its performance as a lithium-ion anode material,with a high rate capability of 400 mAh·g-1at a high current density of 20 A·g-1[73][74][75]。 (Table 1 lists some of the original MOFs material applications).In addition,carbon composite MOFs can also be prepared by using composite graphene oxide(GO)and carbon nanotubes as external carbon sources for performance control,for example,MOFs can be grown on carbon materials such as GO and carbon nanotubes(CNTs)to improve electrochemical performance[76]。 Sung et al.used Co-MOF-74 as an interlayer to composite with multi-walled carbon nanotubes(MWCNTs),and further Used solvothermal method to synthesize Co-MOF-74@MWCNTs as an excellent cathode material for lithium-sulfur batteries[77]。 In addition,graphene,as a single-atom-thick honeycomb carbon lattice sheet with superior electronic conductivity and high specific surface area,can provide active sites by enhancing the interaction with MOFs。

3.2 Carbon materials derived from MOFs

When MOFs are directly used as electrode materials,they usually have problems such as poor conductivity,easy agglomeration,and poor cycle stability.Researchers usually use MOFs as a precursor template,which is calcined in a protective atmosphere to carbonize the internal organic ligands in situ.the graphitized carbon formed can effectively alleviate the volume change and further enhance the conductivity of the material[90]。

3.2.1 Porous carbon material

MOFs can be calcined at high temperature in an inert atmosphere to carbonize the organic ligands in situ to obtain derived porous carbon materials,and the organic ligands containing heteroatoms can also be doped with heteroatoms(such as B,S,P and N)in situ during calcination.the introduction of heteroatoms into the carbon component derived from MOFs can further improve the conductivity and reduce the diffusion resistance of lithium ions in the matrix material[91]。 Carbon materials derived from MOFs usually have lower density,more exposed active sites,and are easier to fully contact with the reaction medium.Liu et al.Proposed an efficient MOFs synthesis scheme to save the cost of porous carbon materials(Fig.8 a),and prepared Zn-BTC by zinc acetate and Na3BTC one-step precipitation method,and further calcined to successfully prepare porous carbon materials(BTCC)for symmetric supercapacitor materials,which also showed good electrochemical performance[92]。 In addition,the interior of hollow porous carbon materials can not only increase the load of active materials and dredge the diffusion pathway,but also provide buffer space for the volume expansion of active materials to achieve sustainable utilization.For example,Li et al.Reported a ZIF-8-derived hybrid hollow nitrogen-doped carbon(HNPC)material(Fig.8B).This hollow nanostructure(Figure 8 e)exhibits excellent electrochemical performance for lithium-sulfur battery sulfur support materials,and its reversible discharge capacity is stable at 562 mAh·g-1after 800 cycles at 2 C rate[93]。

3.2.2 Multilevel structure

the hierarchical nanostructure design of MOFs materials can precisely control the morphology to increase active sites and promote electron transfer,and some composite structures can produce synergistic effects to further improve the electrochemical performance of secondary batteries。
As a dominant hierarchical structure,the core-shell structure can alleviate the performance defects of MOFs-derived materials in the process of application in batteries,thus showing excellent cycling performance.Therefore,by adjusting the types of core-shell composite materials,the active sites can be fully exposed,and the dominant components can play a synergistic role.For the design of core-shell structure,the core-shell structure of MOFs@MOFs can be prepared by using a variety of MOFs,which has great potential in the field of energy storage[94][95]。 core-shell materials with good conductivity and stability can be prepared by nesting and further calcination of the original MOFs.Wang et al.Nested ZIF-8 in ZIF-67 and annealed under Nitrogen protection to obtain the Core-shell structure of NC@GC(Fig.9).nitrogen-doped carbon and graphenized carbon produced by carbonization of two different materials effectively play a synergistic role and show excellent electrochemical performance when used as electrocatalysts[96]。 In addition to calcining to produce graphitized carbon or nitrogen-doped carbon materials,different types of carbon derivative materials can be prepared by regulating the calcination means or adding a carbon source to compound into the spherical shell structure,such as carbon nanotubes,nitrogen-doped carbon,nitrogen-doped carbon nanotubes,reduced graphene oxide,and the like[97][98][99][100]。 in addition,the introduction of multi-metal composite to prepare core-shell structure is also an effective way to enhance the synergistic effect and structural modification.Li et al.Prepared bimetallic Fe/Ni-MIL-53,which was further nested into ZIF-67,and then annealed in a protective atmosphere to prepare Fe/Ni-CoTe@NCFs,in which ZIF-67 was carbonized to form hierarchical hollow N-doped carbon nanoframes(NCFs),and iron and nickel co-doping also produced synergistic effect to improve the electrocatalytic activity[101]。
One-dimensional fibrous carbon materials can be prepared by electrospinning,template method and other methods,which show unique structural advantages in supercapacitors,lithium-ion batteries and other fields[102,103]。 In 2017,Wang et al.Proposed The idea of electrospinning ZIF-8/PAN nanofibers and further carbonizing them into one-dimensional nanoporous carbon fibers.the prepared nitrogen-doped MOFs layered carbon fiber material(NPCF)showed better electrochemical performance than other nitrogen-doped carbon materials when applied to supercapacitor electrode materials[96]。 Zhu et al.Used electrospinning to incorporate Sn-MOF precursors into one-dimensional carbon nanofibers,and further calcined to prepare hierarchical porous Sn@C@CNF materials,which showed excellent performance when applied to anode materials for lithium-ion and sodium-ion batteries[104]。 Recently,Yuan et al.Reported a highly dispersed Co nanoparticle-anchored hierarchical porous N-doped carbon fiber(Co@N-HPCFs)assembled by hollow polyhedra derived from core-shell MOFs(Fig.10)[105]。 the MOFs/PAN nanofibers were prepared by electrospinning.This complex carbon fiber with multi-level porosity can effectively improve The exposure of active sites and promote electron transfer and mass transfer。

3.2.3 Other structures

Song et al.Studied hollow carbon spheres(UHCSs)for modified separators of lithium-sulfur batteries and demonstrated for the first time that such hollow carbon material structures can be used as modified separators due to their unique properties[106]。 Recently,Zhang et al.Used Ni-Co bimetallic MOFs as precursors to prepare NiCo alloy nanoparticles(NiCo@HCS)embedded with hollow carbon spheres(HCSs)by developing a concise template-free method(Figure 11 A),and used them as electrocatalysts for lithium-sulfur battery separator modification to effectively improve the shuttle effect,with an initial capacity of 1377 mAh·g-1at 0.2 C and a capacity decay rate of only 0.056%after 500 cycles at 1.0 C[107]。 Zhang et al.Synthesized carbon-coated CoNiSe2/C nanospheres with bimetallic Ni-Co-MOF as the precursor(Fig.11 B),which made full use of the synergistic effect of bimetals and the structural advantages of carbon nanospheres(specific surface area up to 172.79 m2·g-1）),so that they exhibited superior performance when used as anode materials for lithium-ion batteries,and the reversible discharge capacity was 850.9 mAh·g-1after 100 cycles at a current density of 0.1 A·g-1[108]。
Hong et al.Prepared nitrogen-doped carbon MOFs materials(Zn-TDPAT)with a petal-shaped nanosheet structure(Figure 11C),and three kinds of flower-shaped microporous nitrogen-doped carbon nanosheets with pore sizes<0.6 nm proved to effectively store metastable small sulfur molecules（S2−4）to avoid polysulfide generation[109]。 Qian et al.used PVP as a template to carbonize MOFs at high temperature in an inert atmosphere,and self-doped with low-cost cobalt(Co-SCPC)to prepare porous carbon materials with spherical chrysanthemum-like structure(Fig.11d)for lithium-sulfur batteries.It can effectively inhibit polysulfides while exhibiting excellent electrochemical performance,with high discharge capacities of 1292.5,992.7 and 495.6 mAh·g-1at 0.1 C,1.0 C and 5.0 C rates,respectively,and excellent cycle stability at 1500 cycles at 1 C and 500 cycles at 5 C[110]。

3.3 Metal compounds derived from MOFs.

Appropriate MOFs are selected as precursors,and metal nodes can be transformed into metal compounds(metal oxides,metal sulfides,metal selenides,etc.)Through controlled heat treatment,or further sulfurization,selenization,etc.This kind of metal compound can further enhance the electrochemical performance of MOFs used in energy storage devices while inheriting the original spatial structure of MOFs。

3.3.1 Metal compound composite

MOFs can be transformed into metal oxides,metal oxides@carbon and metal oxide composites after controlled heat treatment.Similarly,metal compounds such as metal phosphides and metal sulfides can also be used to prepare corresponding carbon-based composites by controlled pyrolysis[111]。
In recent years,Co3O4and their composites have shown great potential in various energy storage fields based on their high theoretical energy density and excellent rate capability.As early as 2006,the original Co3O4was used in the research of anode materials for lithium-ion batteries,but due to the problems of insufficient conductivity,poor mechanical strain and slow kinetics of Co3O4,its performance still needs to be further improved[112]。 Subsequent studies have developed a variety of composite materials.Porous Co3O4cubes are used as anode materials for lithium-ion batteries,Co3O4/C porous nanowire arrays,porous Co3O4hollow spheres are used as electrodes for supercapacitors,carbon-based Co3O4dodecahedron with spherical shell structure derived from ZIF-67 is used for lithium-ion or sodium-ion battery anode(Fig.12A),and Co3O4@Co-MOF composite is used for supercapacitors,etc[113][114][115][116][117]。 In terms of other oxide research,Wang et al.Designed to prepare TiO2/C materials(Figure 12B)as anode materials for lithium-ion batteries through a two-step heat treatment method,which still maintained excellent performance under long cycles[118]。
the preparation of metal sulfide-related composite materials Based on the original MOFs is also very popular,and some studies suggest that they are better than oxides in terms of lithium storage capacity,and the preparation methods include one-step sulfidation and stepwise sulfidation.ZIF series and MIL series are mostly used to prepare sulfide precursors,which provide corresponding metal elements and are easy to maintain their structure and Further sulfurize.based on the formation of ZIF-67 on the surface of GO,Yin et al.further vulcanized to prepare CoSx@rGO composite(Figure 12c),which was applied to anode materials for lithium-ion batteries[119]。 Chen et al.Used 1,5-naphthalene disulfonic acid and 4,4'-bipyridine as organic ligands to synthesize a series of sulfonate-based MOFs as precursors.In the further pyrolysis process,1,5-naphthalene disulfonic acid was not only used as a sulfur source for in-situ sulfurization,It can also provide N/S co-doped carbon materials with 4,4'-bipyridine,in which Fe7S8/NSC materials exhibit excellent electrochemical performance when applied to lithium ion and sodium ion anode materials[120]。
Metal phosphides derived from MOFs have been applied in the field of energy storage because of their high stability and conductivity.Liu et al.ZIF-67-derived nanoscale cobalt phosphide S-CoP/CNT composite was further prepared by phosphating,which enhanced the adsorption capacity of polysulfides when applied to lithium-sulfur battery separators,effectively helping the battery to improve its electrochemical performance[121][122]。 In addition to in situ phosphating,researchers have recently found that doping phosphide in MOFs derived materials is also an effective measure to enhance electrochemical performance,and Chen et al.Prepared double carbon materials doped with Ni12P5(nitrogen-doped carbon,carbon nanotube）Zn@NPC-Ni12P5-CNT-n a s cathode materials for lithium-sulfur batteries.It was found that the doping of N12P5increased the active sites for trapping polysulfides,helped the rapid diffusion of lithium ions,and improved the stability[123]。

3.3.2 Polymetal compound

In recent years,single metal compounds are not enough to meet the higher pursuit of conductivity and cycle stability.Multi-metal compounds derived from multi-metal MOFs as precursors can further improve the electrochemical performance by increasing the electrochemical active components,increasing the potential of reaction with ions,and increasing the redox reaction sites.Recently,Zheng et al.Prepared bimetallic Zn/Co-MOF derived porous channel cross structure nanocage oxide by low temperature calcination self-assembly strategy,and further compounded with graphene oxide to obtain rGO/ZnO/Co3O4（(Figure 13A)as anode material for lithium-ion batteries.The specific discharge capacity of rGO/ZnO/Co3O4at a current density of 2 A·g-1is 500 mAh·g-1,which is 3.4 times that of the single metal oxide composite rGO/Co3O4,fully proving the enhancement of electrochemical performance and effective active area of the electrode by the synergistic effect of zinc/cobalt bimetallic oxide and the three-dimensional porous channel heterointerface structure[124]。 Zhao et al.Prepared bimetallic Ni/Co Prussian blue analogue NiCo-PBA as a precursor,and proposed a one-step calcination method to prepare a carbon-doped NiO@Co3O4（Fig.13 B)composite,which can provide a high energy density of 32.6 Wh·kg-1at a power density of 750.0 Wk·g-1and a cycle life of 87.1%after 5000 cycles when used as a supercapacitor electrode material[125]。 Recently,Li et al.Prepared NiCo2O4/carbon composite nanofibers by anchoring MOFs-derived NiCo2O4particles on highly conductive carbon nanofibers,in which MOFs were grown in situ on nanofibers by electrospinning(the template was ZIF-67),and then annealed to prepare beaded NiCo2O4/carbon composite nanofibers,which showed excellent performance when applied to anode materials for lithium-ion and sodium-ion batteries[126]。 the synthesis method of the nickel-cobalt bimetallic oxide doped carbon material is simple,and a new idea is provided for the multi-metal oxide doped carbon material。
Multicomponent metal sulfides and phosphides derived from MOFs have also been studied extensively in recent years.Sun et al.Prepared Fe/Zn-MOF-74 precursor by co-precipitation method,and further sulfurized to obtain sulfur-doped carbon-coated FeS2/ZnS hollow layered sphere material Fe-Zn-S@S-doped-C(Fig.13C),When used as anode materials for lithium-ion batteries,the capacitance was 679 mAh·g-1and 317 mAh·g-1at 1 A·g-1and 5 A·g-1current densities,respectively,and maintained a high capacity of 1321 mAh·g-1after 200 cycles[127]。 Fang et al.Synthesized CoZn-MOFs precursors,and further sulfided and calcined to prepare bimetallic sulfide（Co9S8/ZnS）nanocrystals embedded in hollow nitrogen-doped carbon nanosheets.After optimization,the Co1Zn1-S(600)obtained by calcining at 600°C was screened out,which showed high rate performance and cycle stability in both half-cell and Na3V2(PO4)3||Co1Zn1-S(600)full-cell when applied to sodium-ion battery anode materials[128]。 Dai et al.Prepared bimetallic Ni-Sn-BTC MOF as a precursor by microwave-assisted solvothermal and cation exchange methods,and further obtained Ni-Sn-P@C-CNT derived materials by calcination and phosphating under C2H2/Ar atmosphere.When used as anode materials for lithium-ion batteries,the dual electrochemical components and the in situ grown CNT accelerated the ion transport and improved the cycle stability[129]。 Recently,on the basis of the successful preparation of nickel and cobalt bimetallic compound electrode materials,Ni and others added manganese metal to better activate the 3D electrons of cobalt ions to further enhance the electrochemical performance,and prepared a Mn-Ni-Co sulfide composite material with a double-layer hollow cage structure using ZIF-67 as a template(Fig.13d),which showed excellent performance when applied to supercapacitor electrode materials[130]。

4 Conclusion and prospect

the special structure of MOFs with large specific surface area and high porosity has been widely studied in the field of energy storage.This paper mainly summarizes the applications of MOFs and their derivatives in various energy storage devices(LIBs,SIBs,PIBs,LSBs,ZIBs,SCs),and focuses on the structural modification strategies of MOFs and their derivatives to improve the electrochemical performance.However,there are still some key problems in the practical application of MOFs-related materials in the field of energy storage:
(1)Pure MOFs materials are easy to be modified and subsequently treated to prepare derivative materials to enhance electrochemical performance,but at the same time,many problems such as simple synthesis methods,environmentally friendly and economical raw materials in practical application still need to be solved。
(2)When used in alkali metal batteries,MOFs as anode materials combined with bimetallic synergy,precursor carbonization,macro-structure design,micro-defect introduction and other modification measures effectively improve the capacity and rate performance,but compared with LIBs,MOFs based anode materials of SIBs and PIBs are not widely studied.the large ionic radius of sodium and potassium makes the intercalation and deintercalation kinetics slow,resulting in poor performance.Therefore,adjusting the appropriate pore size to ensure the kinetics with high conductivity and stability has become the next research direction of MOFs derived materials for alkali metal ion battery anode materials。
(3)For metal-chalcogenide batteries,the design of coordinatively unsaturated MOFs,the design of Lewis acidic sites,and the selection of organic ligands containing nitrogen,oxygen,and phosphorus functional groups have significant effects on improving sulfur carriers and polysulfide capture.Compared with MOFs coating,there are some problems such as insufficient sieving ability and weak stability when MOFs are used to prepare LSBs modified separators。
(4)There are few reports on the ultra-long cycle stability of MOFs in various secondary batteries and supercapacitors.At present,MOFs-derived materials emerge in an endless stream,but the preparation scheme is becoming more and more complicated,and the problem of structural collapse often occurs in the preparation process,so it is urgent to explore a simple,safe and stable material preparation strategy。
in order to realize the large-scale application of MOFs related materials In the field of energy storage,future research and modification can be carried out from the following aspects:
(1)the microstructure of MOFs should be intrinsically regulated when designing their modified materials.the theory of coordination unsaturation has shown considerable results in The field of energy storage.The introduction of unsaturated metal nodes in The structure and the regulation strategy between organic ligands will further help MOFs materials to improve their electrochemical performance.The introduction of low-dimensional vacancy defects can also improve the conductivity of MOFs materials。
(2)Increase the application of aMOFs in the field of energy storage.the short-range order can provide a suitable pore environment to alleviate the volume expansion problem,and the abundant active sites accelerate the mass transfer and charge transfer.the introduction of aMOFs into various energy storage devices will help materials to provide more control strategies in microstructure and make up for the shortcomings in the application of original crystalline MOFs。
(3)multi-metal doping Is used to modify MOFs derived materials.based on the mechanism that the multi-metal active center exposes more active sites,increases the ionic reaction potential,and the synergistic effect of multiple electrochemical active components improves the electrochemical performance,the multi-metal doping derived from pure MOFs(ZIF,MIL,etc.)is very effective.Compared with transition metal and precious metal Based materials commonly used in batteries and electrocatalysts,iron,cobalt,nickel,manganese and other elements are more abundant in the earth's crust and are safer and more environmentally friendly。
(4)Enhanced structural design of MOFs-derived materials.Improving the design of crystal structure and morphology and trying to increase a variety of structural composites will help MOFs materials to further improve their electrochemical performance.in addition,MOF-on-MOF-like heterostructures can integrate the dominant components to produce synergistic effects.Such a novel structural design will provide a new direction for MOFs materials used In the field of energy storage,and it is believed that more modified MOFs materials with excellent electrochemical properties will be prepared。
in a word,MOFs and their derivatives have great potential in the field of energy storage,and the performance control strategies and the preparation of composites will also help MOFs to be better used in energy storage devices.It is hoped that the summary of the work related to MOFs materials in this paper can provide help for the research and application of MOFs and their derivatives in the field of energy storage。

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Funding

National Natural Science Foundation of China(51974081)

Fundamental Research Funds for the Central Universities(N2225045)

Liaoning Provincial Applied Basic Research Program Project(23JH2/101600057)

Liaoning Provincial Department of Education Project(zd202006)

Liaoning Provincial Department of Education Project(JYTQN2023385)

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