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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2024 , Vol. 36 >Issue 8: 1217 - 1236

DOI: https://doi.org/10.7536/PC240110

Review

Application of Metal-Organic Frameworks for Battery Separators

  • Pengcheng Xiao ,
  • Saiqun Nie ,
  • Mingliang Luo ,
  • Jiayao Chen ,
  • Fuli Luo ,
  • Tian Zhao , * ,
  • Yue-Jun Liu , *
Expand
  • School of Packaging and Materials Engineering, Hunan University of Technology, Zhuzhou 412007, China
*e-mail: (Tian Zhao);
or (Yue-Jun Liu)

Received date: 2024-01-11

  Revised date: 2024-04-08

  Online published: 2024-07-01

Supported by

National Natural Science Foundation of China(12372245)

Postgraduate Scientific Research Innovation Project of Hunan Province(CX20240908)

Natural Science Foundation of Hunan Province(2024JJ7164)

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Abstract

With the rapid development of the new energy industry,research on different kinds of high-performance batteries has become a hot topic nowadays.As one of the important components of batteries,the separator can effectively prevent direct contact between positive and negative electrodes of batteries and provide favorable channels for ion transport.However,traditional polymer battery separators usually have problems such As insufficient thermal stability,poor ion transport capacity,and poor electrolyte wettability.As a new type of porous crystalline material,metal-organic frameworks(MOFs)have become the current research hotspot for high-performance battery separators due to their high porosity,high specific surface area and excellent thermal stability.in this paper,the applications of various MOFs or MOFs-based materials in battery separators are reviewed,and the advantages and disadvantages of MOFs-based battery separators are comprehensively discussed.Finally,the urgent problems to be solved in the field of MOFs-based battery separators and the development prospects of MOFs in battery separators are presented。

Contents

1 Introduction

2 Lithium-ion battery separators based on MOFs

2.1 Original MOFs based separators

2.2 MOFs composites-based separators

2.3 MOFs derivatives-based separators

3 Lithium-sulfur battery separator

3.1 Original MOFs based separators

3.2 MOFs composites-based separators

3.3 MOFs derivatives-based separators

4 Other types of battery separator based on MOFs

5 Conclusion and outlook

Key words： metal-organic frameworks (MOFs); battery separator; syntheses

Cite this article

Pengcheng Xiao , Saiqun Nie , Mingliang Luo , Jiayao Chen , Fuli Luo , Tian Zhao , Yue-Jun Liu . Application of Metal-Organic Frameworks for Battery Separators[J]. Progress in Chemistry, 2024 , 36(8) : 1217 -1236 . DOI: 10.7536/PC240110

1 Introduction

In the past few decades,due to resource shortage and environmental degradation,social attention to renewable energy storage systems has increased rapidly[1]。 Although clean renewable energy such as solar energy,wind energy,tidal energy and geothermal energy is friendly to the environment,it is affected by the natural environment and has a certain timeliness,so it can not be converted and stored for a long time.Therefore,the development of new renewable energy conversion and storage technologies has become a current research focus[2]。
Among the traditional energy storage technologies,Lithium-ion batteries(LIBs)are favored because of their high energy density and are widely used in mobile phones,computers,portable electronics,and other fields[3]。 However,lithium-ion batteries still face the following challenges,such as lithium dendrite growth piercing the separator,volume expansion,low coulombic efficiency due to continuous electrolyte consumption,and short battery life[4]。 Lithium-sulfur batteries(LSBs)have high energy density and high theoretical specific capacity.Meanwhile,the high abundance of sulfur makes the preparation price of battery materials relatively low[5,6]。 However,the discharge products generated during the operation of lithium-sulfur batteries can reduce the conversion rate of polysulfides and accelerate the shuttle effect of polysulfides,resulting in a serious reduction in the capacity and coulombic efficiency of batteries.in addition,in the process of charging and discharging,lithium dendrites will pierce the separator and cause short circuit of the battery,which seriously limits the commercialization of lithium-sulfur batteries[7,8]。 In other battery systems,such as Aqueous zinc ion batteries(AZIBs),zinc dendrite growth,hydrogen evolution and zinc anode corrosion greatly reduce the life and coulombic efficiency of zinc anode,and insoluble lithium oxides as discharge products of Lithium-oxygen batteries slow down the Redox kinetics.the low energy density of redox flow batteries and the high cost of Vanadium redox flow batteries have limited their further development[9,10][11][12][13]。
in order to solve the problems mentioned above In the battery system,researchers are committed to exploring new battery assembly materials(including positive and negative electrodes,electrolytes and separators)with excellent electrochemical performance[14,15][16]。 Recent studies have shown that functional modification of battery separators can solve some problems that are difficult to improve by modifying electrodes or electrolytes[17]。
As an important part of the battery,the separator plays a key role.the separator can effectively isolate the positive and negative electrodes to prevent short circuit of the battery.the separator has a sufficient pore structure to allow ions to be transported between the positive and negative electrodes to complete the charging and discharging process of the battery.Therefore,the separator needs to have good chemical stability and thermal stability to withstand the high temperature and chemical reaction inside the battery without loss or degradation,ensuring the long-term stability and electrochemical performance of the battery.In addition,the separator must have sufficient pore structure to ensure that ions can be transported quickly to achieve efficient charge-discharge process;the separator needs to have sufficient mechanical strength and stability to withstand mechanical stress during battery assembly and use,while preventing cracking or deformation;the separator needs to have a low conductivity to prevent the self-discharge phenomenon inside the battery,thereby improving the energy density and cycle life of the battery。
Metal organic frameworks(MOFs)are novel porous materials composed of inorganic Metal ions and organic ligands[18⇓⇓⇓~22]。 MOFs have extremely high specific surface area,adjustable pore structure and unsaturated metal sites,which make them show excellent performance in the fields of drug delivery,adsorption,energy storage and transformation[23⇓~25][26⇓~28][29⇓~31][32,33]。
the most prominent features of MOFs are ultra-high porosity and specific surface area,and these properties play a key role In functional applications.the unique pore structure of MOFs makes them have high electrolyte uptake and ion mobility,and their abundant electrochemical active sites make the battery have high capacity.In addition,the MOFs-based composite battery separator has excellent structural stability and enables the battery to have a high electrochemical window during cycling.In addition,the synthesis of MOFs/MOF composites and their derivatives by selecting different metal centers and organic ligands through various post-processing methods,which can be applied to various battery systems,can provide a stable ion transport pathway and suppress the shuttle effect through chemisorption[34⇓~36]。 Therefore,in recent years,the number of scientific research reports based on MOFs battery separators has continued to grow,and their related citation frequency is quite high(Figure 1)。
图1 自2016年以来，以电池用MOFs隔膜为主题的科学文章统计数据（数据来自Web of Science）

Fig. 1 The statistics of scientific articles with the theme of MOFs separators for batteries since 2016 (data from Web of Science)

As of 2024,more than 80 000 MOFs have been reported[37]。 However,not all MOFs or MOFs derivatives are suitable for the battery separator field.First,although MOFs or MOFs derivatives have high specific surface area and abundant pore structure,there are some restrictions on their pore structure when they are used as battery separators,considering the ion transport situation during battery operation.the pore size and shape of MOF materials can affect the diffusion rate of ions in the material.Larger pore size is beneficial to the rapid transport of ions,while smaller pore size may limit the diffusion of ions[38]。 the hydrophilicity and hydrophobicity of the MOF pore will affect the wetting degree of the electrolyte in the pore,and then affect the transport rate of ions in the pore.Some hydrophilic pore channels are favorable for electrolyte wetting,thus promoting ion transport.the pore surface of MOF materials usually has different functional groups,such as amino and carboxyl groups.These functional groups can interact with ions in the electrolyte and affect the diffusion and adsorption behavior of ions in the pores[39]。 the connectivity of pores in MOF materials directly affects the transport path of ions in the materials.Good pore connectivity helps to reduce the hindrance of ion transport and improve the battery performance.By adjusting the pore structure of MOF materials,the ion transmission path of batteries can be optimized,and the charge-discharge performance,cycle life and safety performance of batteries can be improved[40,41]。 When transporting ions,it is necessary to control the pore structure so that it is only suitable for transporting the main ions(Li+for lithium-ion batteries,Zn2+for zinc-ion batteries,etc.),so as to avoid the shuttling of impurity ions between the positive and negative electrodes,thus reducing the ionic conductivity,and thus reducing the capacity and multi-performance of the battery[42]。 Secondly,depending on the type of battery,the stability of MOFs or MOFs derivatives will also be limited,for example,MOFs and MOFs derivatives used in lithium-ion batteries have certain requirements for acid resistance.While MOFs and MOFs derivatives used in aqueous batteries need to have strong water stability,MOFs or MOFs derivatives used in lithium-sulfur batteries need to have strong adsorption properties for polysulfides[43]。 In addition,they should also have good chemical and thermal stability to avoid battery capacity loss due to structural damage of MOFs or MOFs derivatives during battery cycling.Likewise,although the functionalization of MOFs can be achieved by selecting different metal ions and organic ligands,it is necessary to consider whether their chemically grafted derivatives can react with the electrolyte or positive and negative electrodes to generate new impurities and insoluble species,thereby reducing the cycling stability of the battery[44]。 Finally,the loading of MOFs or MOFs derivatives needs to be taken into account when using them to prepare separators or composite separators.Although the addition of MOFs or MOFs derivatives can improve the electrolyte wettability and electrolyte absorption rate of the separator,excessive loading will lead to the reduction of the mechanical strength of the separator,which is difficult to resist dendrite puncture,thus reducing the safety of the battery during cycling[45]。 in this paper,the latest progress of MOFs/MOF composites and their derivatives used in the field of battery separators is reviewed,and the problems to be solved in the field of MOFs-based battery separators and the development prospects of MOFs in battery separators are proposed。

2 MOFs separator for lithium-ion battery

the separator is an important component of lithium-ion batteries,which prevents direct contact between The negative and positive electrodes while providing a favorable channel for lithium ion transport[46⇓~48]。 Traditional polyolefin separators have excellent chemical stability,low price and good mechanical properties,such as Polyethylene(PE)and Polypropylene(PP).However,commercial polyolefin separators have low porosity,poor wettability and low thermal stability,which easily lead to high battery impedance and low energy density,thus reducing the ion mobility,affecting the cycle performance and rate performance of batteries,and limiting their development in the field of high-performance lithium-ion batteries[49,50]。 Bio-based polylactic acid(PLA),Polyacrylonitrile(PAN),Polyvinylidene difluoride(PVDF),Carbon nanotubes(CTNs)and Cellulose separators have been used to improve the performance of lithium-ion batteries and are expected to replace polyolefin separators for commercial mass production[51][52,53][54][54][55]。
MOFs have great potential for applications in materials science due to their unique structures and properties.By rationally choosing the combination of metal ions and organic ligands,the pore size,specific surface area,and stability of MOFs can be tuned to provide customized solutions for battery applications in different environments[56⇓⇓~59]。 The high specific surface area can effectively absorb the electrolyte,prevent the electrolyte from decomposing,and improve the cycle performance of the battery;the open metal sites in the pore channels can chelate with anions in the electrolyte,thereby increasing the mobility of cations;the battery separator with MOFs has higher electrolyte absorption,larger ion mobility,and lower interfacial impedance[45,60]。 In addition,they have excellent electrochemical stability[61,62]。
For lithium-ion batteries,the optimal design of MOFs-based battery separators mainly focuses on improving the safety and cycle stability of batteries.Since the electrolyte used in lithium-ion batteries is an organic solution,the separator needs to have good ionic conductivity,mechanical strength,as well as chemical stability to prevent internal short circuits and battery damage.Therefore,MOFs-based battery separators may need to have high porosity,good ionic conductivity and chemical stability,and certain mechanical strength to meet the requirements of lithium-ion batteries。

2.1 MOFs separator

Coating inorganic nanoparticles on the polyolefin separator can improve the poor thermal stability of the polyolefin separator.the addition of MOFs nanoparticles can improve the performance of polyolefin separator,such as improving the ionic conductivity and accelerating the ion transport rate[63⇓~65]。 Meanwhile,MOFs have excellent chemical stability and provide an additional protective layer for the separator to minimize the physical damage and chemical degradation of the separator,which helps to prolong the service life and reduce the capacity fade of the battery[66]。 In addition,MOFs have good thermal stability,and coating MOFs particles on polyolefin separator can improve the safety performance of batteries[67,68]。 Due to the large specific surface area and abundant pore structure of MOFs,the polyolefin separator coated with MOFs can improve the porosity and electrolyte absorptivity of the separator[52]。 Chen et al.Prepared a ZIF-67/PP separator,which has higher porosity,electrolyte absorptivity,and ionic conductivity compared with the conventional PP separator[61]。 the capacity retention of the battery composed of ZIF-67/PP separator was 84.42%after 100 cycles at room temperature.On this basis,Chen et al.Used water and methanol as solvents to adjust the crystal structure of ZIF-67[62]。 Then the ZIF-67-H2O/PP and ZIF-67-CH3OH/PP separators were prepared by blade coating method,respectively.Compared with the ZIF-67/PP separator,the porosity and electrolyte absorptivity of the ZIF-67-H2O/PP and ZIF-67-CH3OH/PP separators were further improved.In addition,the ZIF-67-CH3OH crystal has the most excellent thermal stability,and the battery assembled from it has a capacity retention of 61.5%after 100 cycles at 55°C 。
Although pure MOFs have some advantages as coating materials for commercial battery separators,such as thermal stability,chemical stability,and excellent adsorption properties,there are also some disadvantages.First,the poor conductivity of pure MOFs means that it is not suitable for high power density batteries.Secondly,pure MOFs particles are prone to aggregation,and inevitable lateral and longitudinal diffusion occurs during the coating process.in addition,the relatively high cost of pure MOFs and the relatively complex preparation technology make it difficult to apply them in large-scale industrial production processes.Finally,pure MOFs may be affected by moisture and oxidation during production and use,resulting in the loss of their properties[69]。

2.2 MOFs composite separator

By compositing MOFs with other materials,not only their structural stability can be improved,but also their electrochemical performance can be enhanced。
Compared with the traditional polyolefin separator,the cellulose nanofiber separator has better thermal stability,excellent electrolyte wettability and electrolyte absorption rate.However,due to hydrogen bonding,cellulose nanofibers(CNFs)are tightly packed with each other,resulting in low porosity of the separator.the porosity and electrolyte absorptivity of CNFs separator can be improved by adding MOF particles,and then the ionic conductivity can be improved.Sun group prepared ZIF-8/CNFs separator by loading ZIF-8 on CNFs[70]。 Compared with the pure CNF separator,ZIF-8 nanoparticles increased the porosity of the separator and effectively prevented the packing between CNFs fibers.In addition,the cell assembled with ZIF-8/CNFs separator has better cycling performance and rate capability(Fig.2)[70]。
图2 ZIF-8/CNFs隔膜的制备机理图以及倍率性能对比图[70]

Fig. 2 Preparation mechanism diagram of ZIF-8/CNFs separator and comparison of rate performance[70]. Copyright 2020, Elsevier

Bacterial cellulose(BC)is an environmentally friendly nanofiber material produced by microbial fermentation.BC fiber has a high aspect ratio,and its fiber surface is rich in hydroxyl groups.The lithium ion battery separator prepared by BC has crosslinking property,is easy to form an ultrafine three-dimensional network structure,and has certain electrolyte affinity and flexibility[71,72]。 However,hydrogen bonding between BC nanofibers reduces the porosity of the separator,resulting in an increase in interfacial impedance and a decrease in ionic conductivity[73,74]。 However,the numerous hydroxyl groups on the surface of BC fibers provide a large number of attachment sites for MOFs,and the addition of MOFs can enhance the porosity of BC and the ability to absorb electrolyte,thereby improving the battery performance.Zhang et al.Reported a BC/ZIF-8 membrane prepared by vacuum filtration[73]。 ZIF-8 nanoparticles were used as a filler to avoid the close packing of BC fibers caused by capillary action during drying,which effectively improved the porosity of the diaphragm.the BC/ZIF-8 separator has higher ionic conductivity and better battery cycling performance than the commercial polyolefin separator(Figure 3).In order to further improve the safety of the battery,Zhang et al.Prepared ZIF-8@BC/ANFs separator on this basis[75]。 the introduction of Aramid fiber(ANFs)effectively enhanced the mechanical strength and thermal stability of the separator.Huang et al.Synthesized a BC/ZIF-67 separator using an in situ growth method[74]。 The uniform dispersion of ZIF-67 nanoparticles on BC can also avoid the close packing of BC caused by capillary action during drying,which effectively improves the porosity and electrolyte retention of the separator.the cell assembled by BC/ZIF-67 separator has better cycling performance。
图3 BC/ZIF-8隔膜的制备示意图、电池循环和倍率性能图以及机理图[73]

Fig. 3 Schematic of BC/ZIF-8 separator preparation, cycling and rate performance diagrams of battery, and mechanism diagram[73]. Copyright 2022, Springer Nature

cellulose acetate(CA)can also be composited with MOFs to prepare lithium-ion battery separators.Polyurethane(PU)is a widely used polymer precursor in the field of electrospinning due to its excellent toughness and chemical stability.It was found that interfiber bridging may be observed in the final product when high concentration or viscous PU solution is used to prepare non-woven fabrics by electrospinning process,which makes PU have obvious advantages in regulating the porosity and pore structure of Cellulose membranes[76,77]。 Deng et al.Prepared CA/PU-UiO-67 separator by electrospinning 7 wt%PU into CA and adding different loadings of UiO-67[78]。 The PU precursor was used to assist CA to form a uniform nanoporous structure,while improving the mechanical properties of the CA membrane.The carbonyl and hydroxyl groups on the CA surface inhibit the anion migration and enhance the Li+mobility.In addition,the synergistic effect between UiO-67 and CA makes the Li+flux uniform,which limits the growth of lithium dendrite.The battery assembled with the CA/PU-UiO-67 separator showed a capacity retention of 78.6%after 900 cycles at 1 C 。
MOFs composites can be complexed with anions by electrospinning,thereby releasing Li+and improving ionic conductivity.For example,Chen et al.Synthesized a UiO-66/PVA(Polyvinyl alcohol,PVA)separator by electrospinning,and assembled the cell using LiPF6and LiClO4as the electrolyte,respectively[66]。 The open metal sites of UiO-66 can adsorb anions,ensure the free movement of Li+in the separator,reduce electrolyte decomposition,accelerate electrode reaction kinetics,and reduce interfacial impedance.The cell assembled with UiO-66/PVA separator exhibited excellent rate and cycling performance 。
the hydrophilicity of Polydopamine(PDA)is different due to The ability of its amino and phenolic hydroxyl groups to polymerize at room temperature and under weak alkaline conditions.Deng et al.Prepared PLA@PDA-ZIF-8 composite separator by PDA-induced MOF self-assembly[51]。 the results show that The PLA@PDA-ZIF-8 composite separator has excellent electrolyte absorptivity and good thermal stability.The capacity retention of the battery assembled with it was 98.78%after 200 cycles at 1 C。
Polyvinylidene difluoride(PVDF)has excellent chemical stability and high mechanical strength,and can be processed in various forms to show different structures.Valverde et al.Prepared PVDF/MOF-808 separator by non-solvent-induced phase separation method,and the addition of MOF-808 nanoparticles increased the porosity of the separator and improved the electrolyte absorptivity and ionic conductivity[79]。 Meanwhile,the internal pore structure of MOF-808 can retain more electrolyte and prevent the battery from capacity fading during high-rate cycling.the cell assembled from PVDF/MOF-808 separator(at 10 wt%loading of MOF-808)has an ultra-high Coulombic efficiency of nearly 100%and better cycling performance compared with the pure PVDF separator(Figure 4)。
图4 PVDF/MOF-808隔膜的机理图以及电池性能图[79]

Fig. 4 Mechanism diagram of PVDF/MOF-808 separator and performance diagram of battery[79]. Copyright 2020, American Chemical Society

Poly(aryl ether benzimidazole)(OPBI)is a polymer with excellent mechanical,thermal and flame retardant properties.the use of OPBI as the separator substrate can improve the safety of the battery during cycling.in addition,the addition of MOF particles in OPBI can enhance the thermal stability and flame retardancy of the separator in addition to the ability to absorb electrolyte.Liu et al.Prepared UiO-66@OPBI separator using a non-solvent-induced phase separation method[80]。 OPBI and UiO-66 cooperate to form a three-dimensional network structure,which has the ability to regulate ion transmission in both directions.Compared with the OPBI separator,the UiO-66@OPBI separator can more effectively regulate the deposition/dissolution behavior of Li+and inhibit Li dendrite growth.The battery assembled by it has good rate performance and cycle performance 。
Li et al.Used the in-situ growth method to grow a continuous and controllable HKUST-1 layer in the PVDF membrane,and cut it to prepare the PVDF-HKUST-1 separator[81]。 The as-prepared PVDF-HKUST-1 composite membrane shows uniform continuous sub-nanometer channels with connected open metal sites and uniform Li+flux.With the advantages of low impedance(~2Ω),high ionic conductivity(0.61 mS·cm-1),and high stripping peak current(0.89 mA·cm-2),the PVDF-HKUST-1 composite separator effectively prevents non-uniform deposition.After 250 cycles,the capacity retention is as high as 81.0% 。
Compared with other high-cost multilayer composite diaphragms at present,such as MXene,Polyimide(PI),cellulose acetate(CA),Nanofibrillated cellulose modified by TEMPO medium(TONFC),Sulfonated nano cellulose(each 17 mm×17 mm diaphragm,the price is 2~30 yuan),most MOFs(ZIF-67,ZIF-8[71,82⇓⇓⇓~86]。 Therefore,as an important component of composite materials,MOF can reduce The cost of composite separator preparation while meeting the requirements of improving battery performance.However,the preparation of MOF composite separator needs to consider whether the MOF particles can be uniformly dispersed.In most cases,researchers usually use dry MOF particles directly mixed with the substrate,and the MOF particles are not uniformly loaded on the substrate,resulting in low loading.Electrospinning can improve the dispersion,but it will increase the cost.the in situ growth method is also only applicable to MOF synthesized at room temperature.In addition,MOFs with hydrophobicity(ZIF series)are often used for compositing with polymer substrate separators,while MOFs with hydrophilicity(HKST-1 series,UiO-66 series)are often used for compositing with cellulose substrates or polar polymers.Hydrophobic MOF has better compatibility with polymers,while hydrophilic MOF compounded with cellulose substrate or polar polymers not only has better compatibility,but also can improve electrolyte wettability and reduce interfacial impedance。
MOFs-based composite separator refers to the embedding of MOFs into traditional polymer or cellulose separator to improve the performance of the separator.the modification layer of MOFs has an important influence on the performance of MOFs-based composite membrane,and the thickness of the modification layer of MOFs directly affects the ion transport performance of the membrane[39]。 A thinner modification layer can provide a shorter ion transmission path,thereby increasing the ion transmission rate.If the modification layer is too thick,it may increase the resistance and reduce the ion transmission rate.the compactness of the modified layer affects the permeability and selectivity of the membrane.If the modification layer is too dense,it may hinder the diffusion of ions,thus reducing the ion transport performance of the separator[87]。 However,moderate compactness can improve the mechanical strength and stability of the membrane.In addition,different types of MOFs modification layers can bring different effects.For example,the modified layer of MOFs with large pore size can improve the permeability of the separator,thereby enhancing the power density of the battery;the modified layer of MOFs with high specific surface area can increase the ion storage capacity of the separator and improve the energy density of the battery。
In addition,some functionalized MOFs modification layers can also improve the hydrophilicity or ion selectivity of the separator,thus further optimizing the performance of the battery[39]。 Therefore,the thickness,compactness and type of the MOFs modification layer in the MOFs-based composite separator will affect the ion transport performance and selectivity of the separator,which needs to be reasonably designed and regulated according to the specific application requirements。

2.3 MOFs derivative membrane

MOFs derivatives usually refer to a kind of porous crystalline material formed by carbonization of MOF at high temperature or introduction of other functional groups on the basis of MOF,such as the introduction of cationic groups—NH2to improve the wettability of separator and electrolyte absorption rate,and the introduction of anionic groups—SO3-to adjust the transmission of Li+,thereby improving the ionic conductivity and battery performance 。
Min et al.Prepared OPBI@UiO-66-S-Li separator by non-solvent-induced phase separation method and cation exchange method[88]。 UiO-66-S-Li synergizes with OPBI to improve the electrolyte wettability and interfacial compatibility of the separator,thereby reducing the interfacial impedance and obtaining high ionic conductivity.Meanwhile,the UiO-66-S-Li particles guide the uniform deposition of Li+,thereby reducing the growth of lithium dendrites.Wang et al.Prepared UiO-66-SO3Li/PVDF separator by coating method[65]。 Its separator has excellent cation selectivity,thermal stability,and high flexibility,which can rapidly transport Li+at high current density while preventing the shuttling of impurity ions.In addition,the separator suppresses the further decomposition of electrolyte and contributes to the formation of a stable SEI layer,which guides the uniform deposition of Li+and thus avoids dendrite growth.Li et al.Fabricated the UIOSOL@PP separator by spray coating,and the UIOSOL coating improved the electrolyte wettability and electrolyte absorptivity of the separator,thus guiding the uniform deposition of Li+[89]。 the cell assembled using The UIOSOL@PP separator showed excellent rate performance and cycling stability(Fig.5)。
图5 UIOSOL@PP隔膜的机理图和电池性能图[89]

Fig. 5 Mechanism diagram of UIOSOL@PP separator and performance diagram of battery[89]. Copyright 2023, Elsevier

Shi et al.Prepared the UiO-66-NH2/PVDF-HFP@GF separator by the coating method,and then synthesized the UiO-66-NH-(CH2)3-SO3-/PVDF-HFP@GF separator by sulfonation and ion exchange[90]。 The—(CH2)3-SO3-group significantly modulates the transport of Li+and improves the selective permeability of the membrane,thereby increasing the ionic conductivity.Barbos et al.Prepared a series of MOF/PVDF-HFP(poly(vinylidene fluoride-hexafluoropropylene)copolymer)separators,including MIL-125/PVDF-HFP,MOF-808/PVDF HFP,and UiO-66-NH2/PVDF-HFP[40]。 The addition of three kinds of MOFs particles improved the porosity,electrolyte absorptivity,electrolyte wettability and ionic conductivity of the separator.Among them,the UiO-66-NH2/PVDF-HFP separator has the lowest impedance,and the battery assembled with the UiO-66-NH2/PVDF-HFP separator has the best rate performance and cycle performance 。
BinSon et al.Combined UiO-66-NH2with PAN nanofibers by electrospinning to prepare GU@PAN separator with high thermal resistance[67]。 UiO-66-NH2can remove impurities(including gas,water,and hydrofluoric acid)that affect battery performance and safety.When the nickel-rich cathode operates under high pressure and high temperature,its diaphragm can effectively inhibit the decomposition of electrolyte and prolong the service life of the cathode.In addition,the excellent cycling stability of 75%is maintained even when 500 ppm of water is present in the electrolyte.The expansion of the electrode caused by gas generation and interface degradation can be reduced to less than 50%by using the separator to assemble a pouch-shaped battery 。
表1 Performance table of MOF-based lithium-ion battery separator

Table 1 The performances of main MOF-based lithium-ion battery separators

Material Cycling performance
(mAh·g−1)		 Rate performance
(mAh·g−1)		 Ionic conductivity
(mS·cm−1)		 Li+ transference number
tLi+		 ref
ZIF-67/PP 104.4 (100th/1 C) 44 (5 C) 1.64 - 61
UIOSOL@PP 155 (600th/1 C) 125 (5 C) 1.09 0.82 89
ZIF-67-H2O/PP 93.92 (100th/1 C) - 0.62 - 62
ZIF-67-CH3OH/PP 104.7 (100th/1 C) - 0.78 - 62
ZIF-8-0.5/CNFs - - 0.41 0.41 70
ZIF-8-1/CNF - - 0.45 0.45 70
ZIF-8-2/CNFs 112 (100th/1 C) 82 (8 C) 1.41 0.50 70
BC/ZIF-8 133 (100th/0.5 C) 102.3 (3 C) 1.12 - 73
ZIF-8@BC/ANFs 140.3 (100th/0.5 C) 114.2 (3 C) 1.60 - 75
LC-UiO-66/PVA - - 2.90 0.59 66
LP-UiO-66/PVA - - 1.90 0.79 66
CA/PU10-UiO-67 - - 1.19 0.59 78
CA/PU30-UiO-67 112 (900th/1 C) - 0.48 0.71 78
PLA@PDA-ZIF-8 138.3 (200th/1 C) - 1.99 - 51
BC/ZIF-67 - - 0.837 - 74
UiO-66-NH-(CH2)3
—SO3-/PVDF-HFP@GF		 76 (3000th/5 C) 45 (20 C) 0.67 0.74 90
MIL-125/PVDF-HFP - 73 (2 C) 2.20 - 40
MOF-808/PVDF-HFP - 64 (2 C) 2.40 - 40
UiO-66-NH2 /PVDF-HFP 80 (100th/1 C) 85 (2 C) 3.10 - 40
PVDF/MOF-808 - 50 (2 C) 3.80 - 79
UiO-66-S@OPBI 94.9 (200th/0.5 C) 97.9 (5 C) 1.21 0.53 88
UiO-66-S-Li@OPBI 107 (200th/0.5 C) 103.1 (5 C) 1.46 0.73 88
GU@PAN 125 (200th/1 C) 58 (10 C) - 0.603 67
PVDF-HKUST-1 121.5 (250th/1 C) 143.7 (2 C) 0.61 - 81
MOF derivatives are usually synthesized by high-temperature carbonization/nitridation for the preparation of cathode and anode composites for lithium-ion batteries to improve battery capacity or cycle life.There are few reports on the preparation of lithium-ion battery separators using MOF derivatives.the addition of MOF derivatives modified by specific functional groups can not only improve the electrolyte absorption of the separator,but also regulate the lithium-ion flux to achieve uniform deposition,resulting In ultra-high stability,ionic conductivity,and capacity of the battery.However,the preparation of MOF-derived composite separator is costly.Therefore,it is necessary to further improve the preparation methods,such as optimizing the structure of MOF derivative materials,realizing the controllable adjustment of functional groups,so that the battery has better cycle performance and rate performance.in addition,the composite application of MOF derivatives and other materials can also be explored[91]。

3 MOFs separator for lithium-sulfur battery

Polysulfide shuttling between electrodes reduces the capacity as well as cycling stability of lithium-sulfur batteries.the separator separates the positive and negative electrodes and provides a lithium ion transport path between the electrodes to ensure that the electrochemical reaction continues.Traditional lithium-sulfur battery separators are mainly polyolefin materials,such as PP,PE,etc.,but polyolefin separators can not avoid the diffusion of polysulfides between electrodes when operating at high current density[92,93]。 Therefore,functional modification of the separator can improve the performance of lithium-sulfur batteries by adsorbing or repelling polysulfides to suppress the shuttle effect[94⇓~96]。 At present,the commonly used materials for lithium-sulfur battery separators include PE,PP,PVDF,PAN,etc[97,98]。
carbon materials have large surface area,strong structural stability and excellent conductivity.Coating carbon materials on the cathode side of the separator can promote electron transport and improve the utilization of the cathode active material.Long-chain polysulfides can be confined in carbon materials by physical adsorption,and the chemisorption of polysulfides can be improved by adding functional groups such as sulfur and nitrogen to carbon materials,thus enhancing the cycling performance of lithium-sulfur batteries[99⇓~101]。 Strong polar transition metal compounds can reduce polysulfide shuttle and improve redox reaction kinetics through chemisorption.However,metal oxides and carbon materials are not flexible enough to be directly used as battery separators,so they are mostly composited with other flexible materials to prepare composite separators[102⇓~104]。 organic materials have the advantages of light weight,flexibility,ductility,electrochemical performance and chemical stability.Common organic materials include Polyaniline(PANI),Polyethylene terephthalate(PET),Polyaryl ether ketone(PEEK),etc.However,not all organic materials contribute to improving the performance of the separator。
MOF,unlike the above inorganic porous materials or organic polymers,has both the rigidity of inorganic materials and the flexibility of organic materials,so it can diversify its structure and obtain different properties by adjusting inorganic metal centers and organic ligands[56,105]。 However,whether as a positive or negative electrode protective layer,the main function of MOF is to guide ions to deposit on the electrode surface and has no practical effect on ion transport.MOFs have a large number of pore structures,good structural stability,which makes them have great advantages in inhibiting polysulfide shuttling and protecting lithium metal anodes.Therefore,the septum becomes the best carrier for MOF to inhibit polysulfide shuttling。
in lithium-sulfur batteries,the optimal design of MOFs-based battery separators mainly focuses on inhibiting the dissolution of sulfur and the shuttling of polysulfides,and improving the conduction performance of lithium ions.MOFs can be used as sulfur immobilization carriers to immobilize sulfur In the electrode through their porous structure,which prevents the dissolution of sulfur and the shuttling of polysulfides,thus improving the cycling stability and energy density of batteries。

3.1 MOFs separator

Inhibition of polysulfide shuttling is a key factor In improving the performance of lithium-sulfur batteries.the appropriate pore structure of MOF can improve the electrolyte wettability and electrolyte absorptivity of the separator,and can also restrict the shuttle of polysulfides between the separators;the groups on the MOF can generate electrostatic repulsion with the polysulfide to further prevent the diffusion of the polysulfide;in addition,MOF particles have excellent thermal/chemical stability,which makes it difficult for polysulfides to penetrate and erode the separator,thus improving the performance of the battery[17,106]。
In order to improve the performance of lithium-sulfur batteries,Suriyakumar et al.Prepared Mn-BTC(BTC=1,3,5 Benzene tricarboxylate-manganese)separators by phase inversion method[107]。 Through electrostatic repulsion,the COO-on the separator traps polysulfides while enhancing the movement of lithium ions,thus inhibiting polysulfide shuttling.The Li-S battery assembled with the Mn-BTC separator exhibited a coulombic efficiency of 94%at 0.1 C and an initial discharge capacity of 1430 mAh·g-1 。
Although conventional polyolefin separators have advantages in terms of cost and mechanical strength,they do not suppress the polysulfide shuttle effect.Li et al.Synthesized a variety of MOF separators to study the factors affecting their inhibition of the polysulfide shuttle effect(including HKUST-1,ZIF-7,Y-FZTB,and ZIF-8)[39]。 the pore size of MOF particles is not the only factor that inhibits the polysulfide shuttle effect;the denser the packing structure of MOF particles,the stronger the ability to suppress the polysulfide shuttle effect.In addition,too high a voltage window may cause the MOF crystal to crack,thereby reducing the ability of its separator to inhibit polysulfide shuttling,thereby reducing the cycle life of the battery。
Qi et al.Prepared MIL-125(Ti)-PP/PE separator by vacuum filtration method(Fig.6)[108]。 Compared with the pure PP/PE separator,the MIL-125(Ti)-PP/PE separator has better electrolyte wettability and electrolyte absorptivity,and the addition of MIL-125(Ti)particles improves the ability of the separator to suppress the polysulfide shuttle effect.In addition,the highly ordered microporous structure of MIL-125(Ti)guides the uniform Li+flux and inhibits the growth of lithium dendrites,which improves the rate capability and cycling performance of the battery.Zang et al.Fabricated the Ni3(HITP)2/PP separator using the interface-induced growth method[109]。 The Ni3(HITP)2separator grown by the interface-induced growth method has higher porosity,higher packing density,and more uniform loading.The Ni3(HITP)2/PP separator has a uniform microporous structure,which can adsorb polysulfides more effectively and suppress the shuttle effect,thus improving the cycle performance of the battery.The cell assembled from the Ni3(HITP)2/PP separator has a capacity retention of 86%after 200 cycles 。
图6 MIL-125(Ti)-PP/PE隔膜机理图以及电化学性能图[108]

Fig. 6 Mechanism diagram of MIL-125(Ti) modified PP/PE separator separator and performance diagram of battery[108]. Copyright 2020, American Chemical Society

Fan et al.Prepared UiO-66/PP separator[110]。 The porous structure of UiO-66 and the strong chemisorption with polysulfides effectively prevent the transport of polysulfides to the lithium anode.Tian et al.Prepared ultrathin Cu2(CuTCPP)/PP membrane by vacuum filtration method[111]。 The highly crystalline and oriented Cu2(CuTCPP)can effectively suppress the polysulfide shuttle and improve the cycling performance of the battery.The battery assembled with the Cu2(CuTCPP)/PP separator showed a capacity retention of 71.1%after 900 cycles at 1 C.Chen et al.Prepared FJU-88/PP and FJU-90/PP membranes by vacuum filtration[38]。 The pore size of the FJU-88/PP separator is too large to effectively suppress the polysulfide shuttle effect.In contrast,the smaller pore size of the FJU-90/PP separator is beneficial for preventing polysulfide shuttling and promoting Li+migration.In addition,the introduction of nitrogen-rich ligands into FJU-90/PP separator increased the nitrogen content of the separator,and more nitrogen atoms cooperated with cobalt atoms to promote the absorption and transformation of polysulfides,thus improving the sulfur utilization.Dang et al.Prepared Ce-UiO-67/GF separator by vacuum filtration method[112]。 the separator has a suitable pore structure,polar functional groups,and Ce catalytic sites,which can effectively adsorb polysulfides and enhance their catalytic conversion,thereby suppressing the shuttle effect.In addition,the oxygen-containing functional groups on the surface of Ce-UiO-67 can guide the uniform deposition of lithium ions,thereby inhibiting the growth of dendrites and improving the battery performance(Table 2)。
表2 Performance table of intrinsic MOF-based lithium-sulfur battery separator

Table 2 The performance of original MOFs-based lithium-sulfur battery separator

Material Initial discharge capacity
(mAh·g-1)		 Cycling performance
(mAh·g-1)		 Sulfur loading
(mg·cm−2)		 ref
Mn-BTC 1450 (0.1 C) 1100 (800th/0.1 C) - 107
Y-FZTB 1101 (0.25 C) 557 (300th/0.25 C) 1.0 39
ZIF-67 1025(0.25 C) 452 (300th/0.25 C) 1.0 39
ZIF-8 989(0.25 C) 403 (300th/0.25 C) 1.0 39
HKUST-1 1032(0.25 C) 197 (300th/0.25 C) 1.0 39
MIL-125(Ti) 1218.3(0.2 C) 726 (200th/0.2 C) 2.0 108
UiO-66 1032 (0.5 C) 586 (500th/0.5 C) 1.5 110
Ni3(HITP)2 1244 (0.2 C) 1139 (100th/0.2 C) 3.5 109
ZIF-8 945 (0.2 C) 581 (100th/0.2 C) 3.5 109
Cu2(CuTCPP) 1200 (0.2 C) 1020 (100th/0.2 C) 2.0 111
FJU-88 955.7 (0.5 C) - 1.0 38
FJU-90 1382.3 (0.2 C) 826.5 (500th/1 C) 1.0 38
Ce-UiO-67 1288 (0.2 C) 919 (500th/1 C) 2.0/7.0 112

3.2 MOFs composite separator

the composite separator Prepared by compounding MOF with other materials can improve its conductivity and adsorption.Separators made from Polystyrene sulfonic acid(PSS)fibers not only have high strength and electrolyte absorption capacity,but also their sulfonic acid groups can be used as functional sites to promote The rapid and uniform deposition of Polystyrene sulfonic acid.The addition of MOF particles can improve the porosity and electrolyte absorption capacity of PSS separator.Guo et al.prepared PSS@HKUST-1/Celgard separator by solid phase transformation method[113]。 Its three-dimensional network structure is beneficial to intercept long-chain polysulfides,and the sulfonic acid group on PSS is also beneficial to promote Li+migration,thus ensuring the fast redox kinetics of the battery.The cell assembled by PSS@HKUST-1/Celgard separator has excellent reversible capacity and cycling performance.Diao et al.Prepared MOF/Nafion multifunctional composite separator using Cu-based metal organic framework and Li-Nafion as raw materials[114]。 Cu-MOF has a uniform porous structure and abundant Lewis acid sites,which not only promotes the uniform distribution of Li+flux,but also exhibits strong chemical interaction with polysulfides and suppresses the shuttle effect.In addition,both the narrow pore size distribution and the negatively charged gap imparted by the SO3-group in the Cu-MOF act as an ionic sieve,restricting the migration of polysulfide anions while promoting the passage of Li+,which synergistically slows down the dendrite growth and polysulfide shuttling 。
Nonpolar carbon materials can physically adsorb polysulfides,but their effectiveness is limited.Modification by adding MOF can improve the adsorption capacity by complexing polysulfides with metal ions and functional groups in MOF.Wu's team fabricated a CNTs@ZIF-8 separator,which improved the cycling performance and reversible capacity of the battery by inhibiting polysulfide shuttling and confining polysulfides to the cathode side[115]。 Song et al.Prepared a Co/NCNS/CNT separator[116]。 Due to the excellent conductivity and high catalytic activity of CoNxand Co nanoparticles,the separator can effectively adsorb polysulfides and catalyze the redox reaction of polysulfides.The batteries assembled with the Co/NCNS/CNT separator showed excellent cycling performance and rate capability at 2 C 。
the solid electrolyte interfacial layer on the surface of the lithium metal anode makes the battery more susceptible to high interfacial resistance,which can reduce the rate capability of the battery and curtail its cycle life.At the same time,the polysulfide shuttle intensifies the anode passivation and leads to the loss of sulfur from the active material.Li et al.Prepared a B/2D MOF-Co separator[117]。 On the anode side,the array of Co-O4groups on the surface of 2D MOF-Co nanosheets can improve the adsorption of Li+through surface O atoms,thus making the Li+flux uniform and further inhibiting the growth of the solid electrolyte interfacial layer;On the cathode side,polysulfides can be effectively anchored by Lewis acid-base interactions.The batteries assembled with B/2D MOF-Co have excellent cycling performance and rate capability 。
Lithium-sulfur batteries have high charge-discharge current density,which leads to large internal temperature difference during operation and shortens their service life.Huang et al.Prepared a PPW/UiO-66@BP separator by electrospinning and vacuum filtration[118]。 Paraffin wax(PW)has a suitable melting point(≈40°C)and a high latent heat(≈212 J·g-1),which acts as a thermal response material to absorb heat and can effectively regulate the heat in the battery.Wrapping them in PAN nanofibers can prevent the dissolution of PW in the liquid electrolyte and ensure the full and repeated utilization of PW.The PPW/UiO-66@BP separator effectively regulates the temperature change of the battery during operation,and at the same time,it can suppress the dendrite growth and the shuttle effect of LiPSs,thus achieving high performance and thermal self-regulation.Therefore,the battery assembled by its separator has excellent cycling performance at different temperatures 。
Poly(m-phenylene isophthalamide)(PMIA)fiber has many covalent bonds and hydrogen bonds,which make the Prepared separator have excellent mechanical strength and thermal stability.Liu et al.prepared a ZIF-L(Co)-PMIA separator by electrospinning[119]。 The uniform micropores and large specific surface area of its diaphragm make it easier to guide Li+deposition,and it can also prevent polysulfide shuttling more effectively.The battery assembled by its separator has excellent rate and cycling performance.Wang et al.Fabricated ZIF-7@PCF separator by in situ growth method[120]。 PCF has a conductive porous carbon skeleton,which can promote the transfer of electrons and ions in the battery.Meanwhile,ZIF-7 provides abundant active sites for polysulfide trapping and conversion.This unique double cross-linked structure design gives the ZIF-7@PCF interlayer excellent performance to suppress the shuttle effect of polysulfides(Fig.7)。
图7 ZIF-7@PCF隔膜的合成机理图以及电化学性能图[120]

Fig. 7 Synthesis mechanism diagram and electrochemical performance diagram of ZIF-7@PCF separator[120]. Copyright 2021, Elsevier

Polyoxometalates(POMs),also known as polyacids,are nanoscale metal-oxygen cluster compounds formed by the high oxidation state of early transition metal ions(such as V,Mo,W,etc.)And oxygen.POM can immobilize polysulfides and accelerate the transfer of soluble higher order polysulfides to Li2S2/Li2S,thus greatly enhancing the reaction kinetics of polysulfids[121]。 Li et al.Used ZIF-67 and H5PW10V2O40·30H2O(PW10V2)as precursors to prepare a composite separator by tightly adsorbing H5PW10V2O40·30H2O(PW10V2))on the surface of ZIF-67 through electrostatic interaction[122]。 The uniform micropores of ZIF-67 can act as a physical barrier against polysulfide shuttling and allow lithium ions to shuttle freely.In addition,PW10V2chemically anchors LiPSs and exhibits excellent catalytic activity toward polysulfides,which is beneficial for preventing soluble polysulfides from reaching the lithium anode and kinetically promoting sulfur redox reaction kinetics 。
MXene is highly conductive,and combining it with MOFs can enhance the surface area and active sites,thereby confining polysulfides and accelerating catalytic conversion.Kiai et al.Prepared a composite separator by coating conductive Ti3C2Tx(MXene)nanosheets/Fe-MOF as well as a Ti3C2Tx(MXene)/Cu-MOF layer on a glass fiber separator using a vacuum filtration method[123]。 the MXene layer with high conductivity and polar surface functional groups can accelerate the polysulfide redox conversion,thereby improving the discharge capacity,coulombic efficiency,cycling stability,and electrochemical conversion reaction of the battery.As a lithium ion sieve,the porous MOF layer can intercept polysulfides,inhibit polysulfide shuttling,and slow down the growth of lithium dendrites。
表3 Performance table of MOF-based composite lithium-sulfur battery separator

Table 3 The performance of MOF composites-based lithium-sulfur battery separator

Material Initial discharge
capacity
(mAh·g-1)		 Cycling per
formance
(mAh·g-1)		 Rate performance
(mAh·g-1)		 ref
PSS@HKUST-1/Celgard 1278 (0.5 C) 775 (500th/0.5 C) 335 (5 C) 113
CNT@ZIF-8 1588.4 (0.2 C) 870 (100th/0.2 C) 583.2 (2 C) 115
Co/NCNS/CNT 1253 (0.1 C) 522 (500th/1 C) 849 (2 C) 116
B/2D MOF-Co 1138 (0.1 C) 580 (500th/0.5 C) 552 (5 C) 117
Co@CoO@N-C/rGO 1385 (0.1 C) 555 (500th/1 C) 555 (2 C) 124
Ni-C(B) 1413.7 (0.05 C) 600 (300th/0.5 C) 556 (1 C) 125
Ni-C(T) 1230 (0.05 C) 472 (300th/0.5 C) 415 (1 C) 125
CoSe2@C-N/CNT 1224 (0.5 C) 761 (300th/1 C) 798 (3 C) 126
ZIF-67@PCF 1221 (0.2 C) 812 (500th/1 C) 661 (5 C) 120
PCN@CNT 1157 (0.1 C) 545 (500th/1 C) 696 (2 C) 127
MXene/PP
/Cu-TCPP		 1275.5 (0.1 C) 687 (100th/0.5 C) 504 (1 C) 128
PPW/UiO-66
@BP		 1344 (0.1 C) 759 (1000th/0.5 C) 525 (4 C) 118
F-ZIF-67-PMIA 1267.5 (0.5 C) 689 (500th/0.5 C) 916 (1 C) 129
F-Cu-BTC-PMIA 1272.2 (0.5 C) 754 (500th/0.5 C) 969 (1 C) 129
ZIF-L(Co)-PMIA 1391.2 (0.2 C) 961 (350th/0.2 C) 774 (2 C) 119
MOF/Nafion - 534.5(300th/0.5 C) - 114
ZIF-67/PW10V2 1637.6 (0.2 C) 1054.6(120th/0.5 C) 802.7(2 C) 122
Cu-MOF/MXene 1203 (0.5 C) 1100 (300th/1 C) 1081(2 C) 123
Fe-MOF/MXene 1297 (0.5 C) 1131 (300th/1 C) 1169(2 C) 123

3.3 MOFs derivative membrane

MOF derivatives are generally divided into MOF chemically modified derivatives and MOF-derived carbon materials.With MOF as the precursor,the material prepared by carbonization at high temperature maintains the excellent properties of MOF[130]。 In organic electrolytes,the porous structure of MOF-derived carbon materials has a significant adsorption capacity for polysulfides,effectively preventing the dissolution of sulfur and polysulfides.In addition,they can provide a fast and stable Li-ion transport channel[35,131⇓~133]。 MOF derivatives are endowed with specific properties by chemical modification of different functional groups on the MOF.For example,different anionic and cationic groups are grafted in the MOF to improve the ionic conductivity,electrolyte uptake of the separator,or to inhibit polysulfide shuttling by chemisorption,thereby improving the battery performance。
The Ce4+metal site in Ce-UiO-66-NH2can interact with polysulfides to promote their redox reactions.At the same time,—NH2can complex with polysulfides,limiting their migration[134,135]。 Su et al.Prepared Ce-UiO-66-NH2separator by coating method[136]。 Li-S batteries assembled with Ce-UiO-66-NH2separators have excellent cycling performance,coulombic efficiency,and capacity retention.Guo et al.Studied the effect of UiO-66 modified by different functional groups on the adsorption capacity of polysulfides,including UiO-66-NH2,UiO-66-COOH,and UiO-66-2OH[137]。 Among them,UiO-66-NH2exhibited the best adsorption capacity for polysulfides and was therefore used to prepare the UiO-66-NH2@graphene separator.It can trap polysulfides in the pores by chemisorption and significantly suppress the shuttle effect.The introduction of a negatively charged group,such as lithium sulfonate(—SO3Li),into the MOF is an effective method that can suppress polysulfide shuttling without reducing lithium ion conductivity.For example,Wang et al.Prepared an MMMS hybrid membrane by a coating method,and—SO3-could effectively regulate the Li+flux and inhibit polysulfide shuttling through electrostatic interaction,and its smaller pore size could also act as a physical barrier to prevent polysulfide shuttling[138]。 Lin et al.Successfully synthesized lithium sulfonate-rich UiO-66(SO3Li)4through multiple grafting reactions,and coated it on polypropylene film to prepare UiO-66(SO3Li)4/PP separator[139]。 The UiO-66(SO3Li)4/PP separator is grafted with more—SO3Li groups than UiO-66 and UiO-66(SO3Li)2,so it has stronger electron affinity and higher lithium ion conductivity.By generating strong electrostatic interactions with polysulfides,the UiO-66(SO3Li)4/PP membrane effectively prevents the shuttling of polysulfides.At the same time,it provides a specific channel for the rapid transfer of Li+,thus preventing the corrosion and dendrite growth of lithium anode and significantly improving the battery performance.Zhao et al.Used the secondary in-situ growth method to prepare the single-side as well as double-side modified UiO-66-(OH)2/PP separator(single-side modified：S-UiO-66-(OH)2/PP,double-side modified D-UiO-66-(OH)2/PP）,respectively[140]。 The UiO-66-(OH)2membrane accelerates the redox kinetics by preventing PS shuttling through the selective sieving effect on neutral LiPS molecules and the charge repulsion effect on PS ions.In addition,the lithiophilic property and the ordered ion channel of the UiO-66-(OH)2film promote the rapid and uniform deposition of Li+,thereby inhibiting the formation of dendrites.The amorphous aMIL-88B modified separator fabricated by Zhang et al.Has more exposed active sites than the original MIL-88B,which can adsorb and catalyze polysulfides more effectively and inhibit the shuttle effect[141]。 The cell assembled using this separator has excellent cycling stability and rate capability at high current density(Fig.8).Chen's group reported an In/Zr-BTB@PP separator prepared by vacuum filtration method[142]。 In,a highly catalytic substance introduced by metal ion exchange,enhances the catalytic ability of the separator for polysulfides,regulates the transport of Li+,and effectively suppresses the shuttle effect.The assembled cell using the In/Zr-BTB@PP separator has excellent cycling stability at high sulfur content and high current density 。
图8 amIL-88B非晶化方案及其电化学性能图[141]

Fig. 8 amIL-88B amorphization scheme and its electrochemical performance diagrams[141]. Copyright 2021, Elsevier

Li et al.Prepared a NiCo2S4@C/PP separator,which had a strong adsorption capacity for polysulfides and effectively inhibited polysulfide shuttling[143]。 At the same time,the NiCo2S4@C/PP separator improves the ionic conductivity,and the battery assembled with it has excellent cycle performance and rate performance.Feng et al.Prepared a Co/CNT@DCNS separator derived from g-C3N4/Co-MOF composite[144]。 The multiple adsorption and catalytic sites in the Co nanoparticles enable the rapid conversion of polysulfides.At the same time,the CNT cross-linked network structure improves the conductivity of the separator and promotes the redox kinetics.In addition,the CxNynanosheets have a large number of defect sites,which enhance their adsorption ability,thereby suppressing the shuttle effect of polysulfides and improving the battery performance.Jin et al.Synthesized a CeO2-C separator that could rapidly adsorb polysulfides and accelerate redox kinetics,inhibiting the shuttle effect[145]。 Its diaphragm has many microporous and mesoporous structures.Li et al.Prepared a MnS/N-C@CNT separator[146]。 ZIF-8-derived N-doped carbon has a variety of microporous and mesoporous structures,which are well suited for polysulfide adsorption.The cell assembled by the MnS/N-C@CNT separator has excellent rate and cycling performance.He et al.Fabricated a Co9S8/Celgard separator by in situ synthesis[147]。 The Co9S8layer has a vertical hollow nanostructure,which can adsorb polysulfides through physical and chemical interactions,thereby inhibiting the shuttle effect of polysulfides and reducing the capacity decay of the battery.The batteries assembled using the Co9S8/Celgard separator have cyclability and rate capability.Fang's group prepared N-C-1000/Celgard(nitrogen doped)and F-N-C-1000/Celgard(fluorine and nitrogen co-doped)separators by pyrolysis and hydrothermal treatment[148]。 The F-N-C-1000 coating increases the porosity of the separator and enhances the physical adsorption capacity,and the co-doping of fluorine and nitrogen further enhances the chemical adsorption of polysulfides,thereby accelerating the catalytic polysulfide conversion,and therefore improving the capacity and cycle stability of the battery.Chuah et al.Prepared an OMNC separator containing a large number of hydroxyl and carboxyl groups,which improved the selectivity for Li+while inhibiting Sn2-permeation due to electrostatic interactions[149]。 In addition,the OMNC separator has high conductivity,which can be used as a secondary current collector to facilitate electron transport,thereby improving the cycling performance of the battery.Li et al.Prepared N,S-Mo2C/C-ACF separator by calcination and acid etching method,which has excellent electrolyte wettability and high ionic conductivity[150]。 Therefore,it can effectively inhibit the shuttle effect of polysulfides and promote the transformation of polysulfides.The cell assembled with the N,S-Mo2C/C-ACF separator has excellent high-rate cycling performance.Peng et al.Prepared a MIL1000/PP separator.The MIL1000 coating contains abundant Fe microparticles,which can effectively inhibit the shuttle effect of polysulfides,and has a certain degree of conductivity,which can promote the conversion of polysulfides,thereby reducing the capacity fade of the battery[151]。 Hao et al.Prepared a Co3O4/ZnO/PE separator based on ZIF-67/ZIF-8,which contains abundant oxygen vacancies and suitable pore size,and can effectively adsorb polysulfides,inhibit their shuttle effect,and promote the catalytic conversion of polysulfides,thereby improving the performance of the battery[152]。
In lithium-sulfur batteries,single-atom catalysts can greatly accelerate the redox reaction of sulfur and inhibit its shuttling by adsorbing polysulfides[153][154]。 Leng et al.Prepared Ni-CoMOF@PAN separator by electrospinning[155]。 The Ni-Co MOF coating provides more adsorption catalytic sites for polysulfides,thereby improving the utilization of sulfur.In addition,its separator has excellent electrolyte absorptivity and thermal stability.The battery assembled from it has excellent rate performance.Ren et al.Prepared Ti3C2Tx/Ni-Co MOF@PP separator by coating method[156]。 The Ti3C2Txnanosheets act as a conductive substrate to provide electrons to the Ni-Co MOF,activating the unsaturated metal sites to catalyze the conversion of LiPSs.Meanwhile,the ultrathin Ni-Co MOF can prevent the stacking of Ti3C2Txnanosheets,and the Ti3C2Tx/Ni-Co MOF@PP separator with heterostructure has superior anchoring and catalytic conversion ability for LiPSs.Shi et al.Pyrolyzed the precursor MOF(ZIF-8)and Fe(acac)3@ZIF-8）at 900°C for 2 H in an inert atmosphere,and then coated on one side of the PP separator to prepare the Fe SAs-NC/PP separator[157]。 In LIB with MoS2electrode,the Fe SAs-NC/PP separator has enhanced reversibility and more stable cycling performance compared with the unmodified PP separator.In addition,the results of visual adsorption experiment and symmetrical cell experiment confirmed that Fe SAs-NC could adsorb soluble LiPSs and catalyze the slow conversion.Razaq et al.Synthesized bimetallic MOFs(Fe-ZIF-8)with nanoflower structure at 35°C,and cast them on PP separator to prepare Fe-ZIF-8/PP separator[158]。 Fe-ZIF-8 provides a selective channel,which effectively inhibits the migration of lithium polysulfides and regulates lithium ion transport.In addition,the large number of active sites of Fe-ZIF-8 facilitates the conversion of lithium polysulfides.Pang et al.Prepared sulfonic acid functionalized S-MIL-101 separator by casting method[159]。 the functionalized sulfonic acid group not only accelerates the conduction of lithium ions,but also repels polysulfide anions through electrostatic interaction,thereby improving the cycling stability of the battery(Table 4)。
表4 Performance table of MOFs derivative-based lithium-sulfur battery separator

Table 4 Performance of MOF derivatives-based lithium-sulfur battery separator

Material Initial discharge
capacity
(mAh·g−1)		 Cycling performance
(mAh·g−1)		 Rate performance
(mAh·g−1)		 ref
Ce-UiO-66-NH2 1366 (0.2 C) 627 (300th/2 C) 653.3 (2 C) 136
UiO-66-NH2@
graphene		 1598 (0.2 C) 800 (100th/1 C) 705 (3 C) 137
UiO-66(SO3Li)4 1493.3 (0.1 C) 457 (1000th/1 C) 730.1 (2 C) 139
aMIL-88B 1508 (0.1 C) 740 (500th/1 C) 610 (5 C) 141
In/Zr-BTB@PP 1067.7 (0.2 C) 679 (500th/2 C) 637.7 (5 C) 142
NiCo2S4@C 1383 (0.1 C) 700 (200th/2 C) 850 (2 C) 143
Co/CNT@DCNS 1235 (0.2 C) 691 (500th/0.5 C) 870 (2 C) 144
Co8S9 1385 (0.1 C) 1190 (200th/0.1 C) 428 (2 C) 147
CeO2-C 1240 (0.1 C) 520 (500th/0.5 C) 531 (1 C) 145
N-C-1000 1200 (0.2 C) / 531 (1 C) 148
F-N-C-1000 1250 (0.2 C) 640 (500th/2 C) 500 (5 C) 148
OMNC 1257.1 (0.5 C) 736 (300th/0.5 C) / 149
N,S-Mo2C/C-ACF 1200 (0.2 C) 432 (600th/1 C) 630 (5 C) 150
MnSN-C@CNT 1181 (0.1 C) 500 (500th/0.5 C) 627 (1 C) 146
MIL1000 1244.6 (0.1 C) 570 (500th/1 C) 739.1 (2 C) 151
Co3O4/Zno/PE 875.5 (0.5 C) 500 (400th/0.5 C) 666.7 (1 C) 152
MMMS 1069 (0.1 C) 580 (500th/0.5 C 552 (5 C) 138
Ni-Co MOF@PAN 1560 (0.1 C) 242 (2000th/2 C) 532 (10 C) 155
Fe SAs-NC/PP 1052 (0.1 C) 789 (200th/0.2 C) 420 (5 C) 157
Fe-ZIF-8/PP 863 (0.5 C) 555 (100th/0.1 C 746 (3 C) 158
Ti3C2Tx/Ni-Co MOF@PP 1260 (0.2 C) 91% (350th/0.5 C) 660 (2 C) 156
S-UiO-66-(OH)2/PP 1235 (0.2 C) 733.45 (500th/1 C) 623 (5 C) 140
D-UiO-66-(OH)2/PP 806.2 (0.2 C) 750.7(100th/0.2 C) / 140
S-MIL-101 1444.6 (0.2 C) 990.4(100th/0.2 C) 803.5 (3 C) 159

4 MOFs separator for other types of batteries

Although MOF is widely used in lithium-sulfur batteries and lithium-ion battery separators,it has been less studied as a battery separator in other battery systems.the cost of MOF is still high compared with traditional separator materials such as polypropylene,which may affect its competitiveness in large-scale commercial applications.Studies on MOF in other battery systems are still relatively few,and more experimental data are needed to verify its performance as a separator in other battery systems.the battery separator of aqueous zinc-ion battery is usually made of Glass fiber(GF).GF has high porosity and good water stability,which can reduce The ion transport resistance in The electrolyte.However,GF has low mechanical strength and cannot resist dendrite puncture[160]。 Yang et al.Prepared a Zn-BTC separator,which can adjust the electrolyte solvation structure and produce a highly aggregated electrolyte layer,while effectively inhibiting the I3-shuttle and preventing the continuous consumption of Zn(OH)2,thus triggering the oxygen evolution reaction[161]。 MOF has promising applications in aqueous zinc-ion batteries due to its porous and functionalized characteristics[162]。 UiO-66 has high specific surface area,hydrothermal stability,and diverse characteristics,showing great advantages in aqueous zinc-ion battery applications.the high specific surface area and abundant pore structure of UiO-66 enable the electrolyte to permeate uniformly and effectively reduce the local current density,thereby reducing the interfacial resistance and enhancing the cycling stability and rate capability of the battery.Maeboonruan et al.Prepared UiO-66/GF and MOF-808/GF composite separators by dip-coating UiO-66 and MOF-808 solutions into GF[163]。 The battery assembled by its separator has excellent cycling stability and long service life.Song et al.Prepared UiO-66-GF separator by in-situ hydrothermal growth method[164]。 the UiO-66 functionalized glass fiber separator can accelerate the transport of charge carriers and provide a uniform electric field distribution on the surface of the zinc anode.the zinc anode shows a preferred orientation of(002)plane under the control of the UiO-66-GF separator,which effectively inhibits the dendrite growth and improves the cycle stability of the battery。
The redox kinetics of lithium-oxygen（Li-O2）batteries are sluggish,and the insoluble solid discharge product,lithium oxide,reduces battery life and rate capability[165]。 Qiao's group prepared HKUST-1@PVDF-HFP/Celgard separator by in situ synthesis method[166]。 The separator can effectively inhibit Redox mediators(RM)from entering the anode side,thereby reducing the corrosion of the lithium anode.In addition,compared with Celgard separator and glass fiber separator,the separator has excellent electrolyte absorption capacity,and the battery assembled with the separator has high specific capacity,low overpotential,and excellent high current density cycling performance and rate capability.Deng et al.Prepared a ZIF-7 separator by a coating method and assembled it into an organic Li-O2cell by combining it with a lithium-based organic liquid anode and an oxygen cathode with high ionic conductivity,low working potential,and high safety[167]。 the ZIF-7 separator not only separates the liquid anode,but also limits the penetration of redox mediators on the cathode side,thereby suppressing the crossover effect.the three-dimensional pore structure of the ZIF-7 separator allows fast ion transport,and the SEI layer on its separator surface helps the Bp-Li anode to establish a more stable interface.In addition,Bp-Li anodes have high electrical and ionic conductivity,so the batteries assembled from them have excellent cycling performance at high current density(Fig.9)。
图9 ZIF-7隔膜的机理图以及电化学性能图[167]

Fig. 9 Mechanism diagram and electrochemical performance of ZIF-7 separator[167]. Copyright 2020, John Wiley and Sons

Nonaqueous redox flow batteries have the advantages of high efficiency,low cost and long life.However,they typically use inorganic ceramic or organic polymer separators,which are expensive,fragile,and unstable,and organic polymer separators are easy to manufacture on a large scale but have low ionic conductivity in non-aqueous systems.Peng et al.Prepared CuBTC/Celgard separator using in situ synthesis method[168]。 the in situ grown CuBTC separator reduces the effective pore size,thereby suppressing the cross-contamination of large active species,and the CuBTC/Celgard separator is significantly more selective for ferrocene molecules than the conventional Celgard separator,which in turn accelerates the redox kinetics.the gradient distribution of CuBTC crystals in the separator not only improves the selectivity of the active material carrier,but also ensures the efficient ion passage rate.the battery assembled by the separator has excellent cycle performance and service life.the MOFs-based composite membrane prepared by the coating method has poor uniformity,and the MOF particles are easy to agglomerate in a large area,which hinders the transmission of ions.in addition,the binding force between the directly coated MOFs and the substrate material is weak,and it is easy to fall off during the cycle of the battery,thus affecting the cycle stability of the battery.the MOFs-based composite separator prepared by the in-situ growth method has better uniformity and stronger binding force,and the MOF particles are uniformly dispersed,which can more effectively guide the ion deposition and increase the cycle stability of the battery。
Vanadium redox flow batteries(VFB)can be used to store energy,but their high cost limits further development.Perfluorinated ionic polymer proton exchange membranes have poor vanadium barrier properties,and non-fluorinated polymers,such as sulfonated polyetherketone(SPEEK),sulfonated polyethersulfone(SPES),and sulfonated polyimide(SPI),have excellent vanadium barrier properties,but their proton conductivity is low.Yang et al.Fabricated phosphotungstic acid(PWA)coupled UiO-66-NH2composite Nafion diaphragm（Nafion-(UiO-66-NH2@PWA）)by casting method[169]。 The separator has excellent vanadium barrier properties and can effectively prevent vanadium penetration.In addition,the ion selectivity of the modified composite separator is better than that of the Nafion separator.Coupling PWA with UiO-66-NH2can effectively reduce PWA leakage,and the ultra-strong proton conductivity of PWA can compensate the proton conductivity of the modified composite separator.The battery assembled by it has excellent cycle performance and low self-discharge rate.Although MOF-supported phosphotungstic acid can improve the conductivity of the proton exchange membrane,highly water-soluble phosphotungstic acid(HPW)still leaches in the presence of water due to insufficient electrostatic interaction strength.Zhai et al.Used a sintering process to chemically combine HPW with MIL-101-NH2,allowing HPW to fill the pore channels of MIL-101-NH2,thereby reducing leaching[170]。 It not only reduces the pore size,but also effectively prevents the penetration of vanadium ions and provides an effective pore channel for proton transport.the composite proton exchange membrane SPEEK/HMN-6 has a significantly higher proton conductivity and further increases the wettability of the membrane。
Rechargeable organic batteries have low cost,good sustainability and easy mass production.However,the problems of severe electrode dissolution and shuttling of organic redox intermediates reduce the capacity and cycling stability of batteries,thus limiting their further development.Bai et al.Prepared ZIF-8 gel films using a coating method[171]。 the pore structure of the single-component ZIF-8 gel membrane not only avoids the cross-contamination of the positive and negative electrodes caused by the intermediate shuttle,but also improves the lithium flux,thereby improving the selective permeability of its separator.the battery assembled by the separator has excellent cycle performance and rate performance.However,not all MOFs can be used to prepare single-component battery separators,MOF particles have poor adhesion and crack after drying,and single-component MOF separators have poor mechanical strength and can not resist dendrite puncture.the feasibility of gel film experiment is difficult and the reproducibility is low.Therefore,how to realize the batch preparation of single-component MOF gel membranes is still a difficult problem。
While conventional battery separators are typically made of polymer materials,MOFs have multiple advantages.First,the MOF has a porous structure,which can provide a better ion transport pathway,thereby improving the power density and cycle life of the battery.Second,the MOF is highly tunable and can be optimally designed for different cell requirements to achieve better performance.in addition,MOF has excellent mechanical stability and chemical inertness,which can improve the durability of battery separators.However,MOF also has some limitations.the synthesis time of MOF is long,and the stability and durability of MOF still need to be greatly improved in order to meet the long-term needs of battery applications.to fully study the potential of MOF in the field of battery separator,the scope of application still needs to be expanded and developed。
For other types of batteries,the optimal design of MOFs-based battery separators will also be adjusted according to their specific battery chemical reactions and operating conditions[172]。 For example,In aqueous zinc-ion batteries,MOFs-based battery separators need to have good ionic conductivity to promote the migration of zinc ions between the positive and negative electrodes and maintain the high efficiency of the battery.At the same time,because aqueous zinc-ion batteries use water as electrolyte,the separator also needs to have high chemical stability to resist water corrosion and dissolution.In lithium-oxygen batteries,MOFs-based battery separators need to have good oxygen permeability to promote oxygen transport between the electrode and the electrolyte and improve the discharge performance of the battery.In addition,the separator can also be designed to catalyze the oxygen reduction reaction to improve the efficiency and cycling stability of the battery.In redox flow batteries,MOFs-based battery separators need to have good ionic conductivity to facilitate the transport of redox solution between the anode and cathode.In addition,the separator also needs to have appropriate selectivity to prevent cross-contamination between mixed flowing electrolytes and maintain high efficiency and cycling stability of the battery.In rechargeable organic batteries,MOFs-based battery separators need to have good solution permeability to promote the transport of organic electrolytes between the positive and negative electrodes and improve the charge-discharge performance of the battery.At the same time,due to the complex chemical properties of organic electrolytes,the separator also needs to have high chemical stability to maintain the long-term cycle stability of the battery(Table 5)。
表5 Comparison of advantages and disadvantages of MOFs-based battery separator preparation methods

Table 5 Comparison of advantages and disadvantages of various preparation methods for the MOFs-based separators

制备方法 优势 劣势
涂布法 简单高效，易于大规模生产 需要考虑MOF颗粒与基底材料之间的结合力和界面相容性
真空抽滤法 适用于实验室小规模制备，简单高效 仅适用于纤维素基质或少数聚合物基质，且MOF颗粒必须均匀地分散在基质悬浮液中
原位生长法 制备过程简单，MOF颗粒分散均匀，不易从基底材料上脱落 仅适用于可在室温下制备的MOF，如ZIF-8、ZIF-67、UiO-66等
静电纺丝法 适用于大多数MOF 部分电纺丝系统需要在高腐蚀性或剧毒溶剂中进行，且有机溶剂成本高，不易回收，容易造成环境污染
非溶剂诱导相分离法以及热致相分离法 制备过程简单、快速，不需要复杂的设备和条件 仅适用于少数聚合物体系，且溶剂会造成环境污染

5 Conclusion and prospect

as an important part of the battery,the separator can effectively prevent internal short circuit,improve battery safety and promote battery performance.At present,the development of battery separator has entered a new stage,and the selection,preparation process and structural design of separator materials are constantly improving and innovating.Especially In the field of new energy,the research and progress of battery separator has become an important research direction.the traditional polyolefin and glass fiber separator is not resistant to dendrite puncture,has poor cycle stability,can not regulate ion transmission,and reduces the electrochemical performance of the battery to a certain extent;Even diaphragms prepared from cellulose cannot avoid these problems due to non-uniform pore size.as a new material with excellent ion transport properties,chemical stability,and modifiable characteristics,MOF can replace traditional polymer separators in the fields of lithium-ion batteries,lithium-sulfur batteries,aqueous zinc-ion batteries,and supercapacitors.in recent years,MOF has received high attention in the field of electrochemistry,including for the preparation of battery cathode and anode composites to improve battery capacity,as a coating to regulate ion flux and guide dendrite growth,It is used As an electrolyte additive to improve ion transport and avoid dead battery due to ion deposition,and is used to prepare battery separators to improve ion conductivity and ion transference number.in particular,MOF has the following advantages when used as a battery separator。
(1)Tunability:By precisely controlling the type and ratio of metal ions and organic ligands,MOF can adapt to different battery requirements and improve battery performance.For example,changing the pore size and surface chemistry of the MOF can be used to select and optimize ion transport rates。
(2)excellent chemical/thermal stability:the MOF can maintain Excellent chemical and thermal stability over a wide temperature range,therefore,The MOF separator can maintain stable ion transport performance during battery use and prolong battery life。
(3)ion transport characteristics:The unique pore structure and high specific surface area of MOF provide excellent ion transport pathways,which can accelerate ion transport and improve cell efficiency。
Despite the aforementioned advantages of MOF as a battery separator,there are still some problems and challenges in various novel batteries.Unmodified MOF particles have poor conductivity and structural stability during battery operation,and most MOFs are damaged in water or acid-base environment,resulting in poor cycling stability.aqueous zinc-ion batteries must consider the water stability of MOF,which greatly limits the types of MOF separators that can be used in Aqueous zinc-ion batteries.Although some two-dimensional conducting MOFs have been developed,they have not achieved the expected capacity and stability when used as high-rate electrode materials in batteries.in addition to the development of new MOFs with high conductivity and stability,functional modification by grafting desired atoms or groups into the MOF interior can also improve its performance.in contrast,researchers believe that MOF derivatives with higher conductivity and better stability are promising materials for various battery applications.However,the self-aggregation of MOF derivative particles and the deterioration of microstructure can lead to the decline of electrochemical performance during long-term cycling,so there are few reports on the preparation of battery separators from MOF derivatives in many new batteries.the main applications of MOF battery separators are to regulate ion transport and dendrite growth,reduce the shuttle effect to avoid capacity loss,and improve the capacity retention and rate capability of batteries.Although many excellent battery separators cannot be produced on a large scale at present,the research on MOF battery separators should continue to increase.for example,the following aspects can be carried out:(1)further optimize the structure and synthesis method of MOF,improve its specific surface area,porosity and stability,introduce specific groups through grafting modification to improve electrochemical performance,improve ion selective permeability by improving pore size,and screen MOF suitable for different batteries to meet the requirements of electrochemical applications;(2)Deeply study the application mechanism and effect of MOF in different types of batteries,optimize its physical and electrochemical properties,and improve the performance and cycle life of batteries;(3)the future research of MOF battery separator should also emphasize the optimization and innovation of the preparation process of MOF and other materials(such as polymers or carbon nanotubes),reduce the process cost,maximize the role and synergy of the components in the composite separator,to prepare battery separators with various functions,and broaden the application scope of MOF in the energy storage industry。

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]
Dunn B, Kamath H, Tarascon J M. Science, 2011, 334(6058): 928.

[2]
Hoseini S S, Seyedkanani A, Najafi G, Sasmito A P, Akbarzadeh A. Energy Storage Mater., 2023, 59: 102768.

[3]
Manthiram A. ACS Cent. Sci., 2017, 3(10): 1063.

[4]
Lee Y G, Fujiki S, Jung C, Suzuki N, Yashiro N, Omoda R, Ko D S, Shiratsuchi T, Sugimoto T, Ryu S, Ku J H, Watanabe T, Park Y, Aihara Y, Im D, Han I T. Nat. Energy, 2020, 5(4): 299.

[5]
Seh Z W, Sun Y M, Zhang Q F, Cui Y. Chem. Soc. Rev., 2016, 45(20): 5605.

[6]
Manthiram A, Fu Y Z, Chung S H, Zu C X, Su Y S. Chem. Rev., 2014, 114(23): 11751.

[7]
Zhang L L, Liu D B, Muhammad Z, Wan F, Xie W, Wang Y J, Song L, Niu Z Q, Chen J. Adv. Mater., 2019, 31(40): 1903955.

[8]
Zhang X, Xie H, Kim C S, Zaghib K, Mauger A, Julien C M. Mater. Sci. Eng. R Rep., 2017, 121: 1.

[9]
Jia H, Wang Z Q, Tawiah B, Wang Y D, Chan C Y, Fei B, Pan F. Nano Energy, 2020, 70: 104523.

[10]
Tang B Y, Shan L T, Liang S Q, Zhou J. Energy Environ. Sci., 2019, 12(11): 3288.

[11]
Matsuda S, Ono M, Asahina H, Kimura S, Mizuki E, Yasukawa E, Yamaguchi S, Kubo Y, Uosaki K. Adv. Energy Mater., 2023, 13(11): 2203062.

[12]
Yan L G, Li D, Li S Q, Xu Z, Dong J H, Jing W H, Xing W H. ACS Appl. Mater. Interfaces, 2016, 8(51): 35289.

[13]
Lourenssen K, Williams J, Ahmadpour F, Clemmer R, Tasnim S. J. Energy Storage, 2019, 25: 100844.

[14]
Xu X J, Liu J, Liu J W, Ouyang L Z, Hu R Z, Wang H, Yang L C, Zhu M. Adv. Funct. Mater., 2018, 28(16): 1870108.

[15]
Yang T, Xu X J, Yang Y, Fan W Z, Wu Y X, Ji S M, Zhao J W, Liu J, Huo Y P. Energy Mater. Adv., 2024, 5: 0078.

[16]
Yang Y, Yao S Y, Wu Y W, Ding J Y, Liang Z W, Li F K, Zhu M, Liu J. Nano Lett., 2023, 23(11): 5061.

[17]
Li C, Liu R, Xiao Y, Cao F F, Zhang H. Energy Storage Mater., 2021, 40: 439.

[18]
Xu G Y, Zhu C Y, Gao G. Small, 2022, 18(44): 2203140.

[19]
Dong A R, Chen D D, Li Q P, Qian J J. Small, 2023, 19(10): 2201550.

[20]
Zhang L T, Liu M L, Fang Z L, Ju Q. Coord. Chem. Rev., 2022, 468: 214641.

[21]
Zhao T, Li S H, Xiao Y X, Janiak C, Chang G G, Tian G, Yang X Y. Sci. China Mater., 2021, 64(1): 252.

[22]
Zou M M, Dong M, Zhao T. Int. J. Mol. Sci., 2022, 23(16): 9396.

[23]
Zheng H Q, Zhang Y N, Liu L F, Wan W, Guo P, Nyström A M, Zou X D. J. Am. Chem. Soc., 2016, 138(3): 962.

[24]
Teplensky M H, Fantham M, Poudel C, Hockings C, Lu M, Guna A, Aragones-Anglada M, Moghadam P Z, Li P, Farha O K, Bernaldo de Quirós Fernández S, Richards F M, Jodrell D I, Kaminski Schierle G, Kaminski C F, Fairen-Jimenez D. Chem, 2019, 5(11): 2926.

[25]
Zhao T, Nie S Q, Luo M L, Xiao P C, Zou M M, Chen Y. J. Alloys Compd., 2024, 974: 172897.

[26]
Qasem N A A, Ben-Mansour R, Habib M A. Appl. Energy, 2018, 210: 317.

[27]
Fakhraei Ghazvini M, Vahedi M, Najafi Nobar S, Sabouri F. J. Environ. Chem. Eng., 2021, 9(1): 104790.

[28]
Li J X, Chang G G, Tian G, Pu C, Huang K X, Ke S C, Janiak C, Yang X Y. Adv. Funct. Mater., 2021, 31(30): 2102868.

[29]
Zhou J E, Xu Z H, Li Y L, Lin X M, Wu Y B, Zeb A, Zhang S G. Coord. Chem. Rev., 2023, 494: 215348.

[30]
Li X R, Yang X C, Xue H G, Pang H, Xu Q. EnergyChem, 2020, 2(2): 100027.

[31]
Bai S Y, Sun Y, Yi J, He Y B, Qiao Y, Zhou H S. Joule, 2018, 2(10): 2117.

[32]
Hou C C, Xu Q. Adv. Energy Mater., 2019, 9(23): 1801307.

[33]
Li Z Q, Ge X L, Li C X, Dong S H, Tang R, Wang C X, Zhang Z W, Yin L W. Small Meth., 2020, 4(3): 1900756.

[34]
Yuan N, Sun W D, Yang J L, Gong X R, Liu R P. Adv. Mater. Interfaces, 2021, 8(9): 2001941.

[35]
Phung J, Zhang X Z, Deng W J, Li G. Sustain. Mater. Technol., 2022, 31: e00374.

[36]
Zhou J E, Chen J H, Peng Y H, Zheng Y Q, Zeb A, Lin X M. Coord. Chem. Rev., 2022, 472: 214781.

[37]
Freund R, Canossa S, Cohen S M, Yan W, Deng H X, Guillerm V, Eddaoudi M, Madden D G, Fairen-Jimenez D, Lyu H, Macreadie L K, Ji Z, Zhang Y Y, Wang B, Haase F, Wöll C, Zaremba O, Andreo J, Wuttke S, Diercks C S. Angew. Chem. Int. Ed., 2021, 60(45): 23946.

[38]
Chen Y L, Zhang L J, Pan H, Zhang J D, Xiang S C, Cheng Z B, Zhang Z J. J. Mater. Chem. A, 2021, 9(47): 26929.

[39]
Li M L, Wan Y, Huang J K, Assen A H, Hsiung C E, Jiang H, Han Y, Eddaoudi M, Lai Z P, Ming J, Li L J. ACS Energy Lett., 2017, 2(10): 2362.

[40]
Barbosa J C, Gonçalves R, Valverde A, Martins P M, Petrenko V I, Márton M, Fidalgo-Marijuan A, Fernández de Luis R, Costa C M, Lanceros-Méndez S. Chem. Eng. J., 2022, 443: 136329.

[41]
Chong Y L, Zhao D D, Wang B, Feng L, Li S J, Shao L X, Tong X, Du X, Cheng H, Zhuang J L. Chem. Rec., 2022, 22(10): e202200142.

[42]
Song X, Xu X J, Liu J. ChemNanoMat, 2023, 9(10): e202300246.

[43]
Li Z, Sun L, Wang K, Zhang Y. Mater. Today Sustain., 2023, 22: 100392.

[44]
Liu C C, Wu B R, Liu T, Zhang Y X, Cui J W, Huang L J, Tan G Q, Zhang L, Su Y F, Wu F. J. Energy Chem., 2024, 89: 449.

[45]
Ye Z Q, Jiang Y, Li L, Wu F, Chen R J. Nano Micro Lett., 2021, 13(1): 203.

[46]
Zhong S J, Yuan B T, Guang Z X, Chen D J, Li Q, Dong L W, Ji Y P, Dong Y F, Han J C, He W D. Energy Storage Mater., 2021, 41: 805.

[47]
Li S, Zhu W C, Tang Q S, Huang Z Z, Yu P T, Gui X F, Lin S D, Hu J W, Tu Y Y. Energy Fuels, 2021, 35(16): 12938.

[48]
Zhang L P, Li X L, Yang M R, Chen W H. Energy Storage Mater., 2021, 41: 522.

[49]
Dai X K, Zhang X M, Wen J W, Wang C X, Ma X L, Yang Y, Huang G Y, Ye H M, Xu S M. Energy Storage Mater., 2022, 51: 638.

[50]
Xing J X, Li J Y, Fan W X, Zhao T Q, Chen X Y, Li H Q, Cui Y J, Wei Z Z, Zhao Y. Compos. Part B Eng., 2022, 243: 110105.

[51]
Deng L X, Cai C Y, Huang Y Z, Fu Y. Microporous Mesoporous Mater., 2022, 329: 111544.

[52]
Yang L Y, Cao J H, Cai B R, Liang T, Wu D Y. Electrochim. Acta, 2021, 382: 138346.

[53]
Huang D, Liang C, Chen L N, Tang M, Zheng Z J, Wang Z B. J. Mater. Sci., 2021, 56(9): 5868.

[54]
Fu Q S, Zhang W, Muhammad I P, Chen X D, Zeng Y, Wang B T, Zhang S Y. Microporous Mesoporous Mater., 2021, 311: 110724.

[55]
Du R, Wu Y, Yang Y, Zhai T, Zhou T, Shang Q, Zhu L, Shang C, Guo Z. Adv. Energy Mater., 2021, 11(20): 2100154.

[56]
Peng Y, Xu J, Xu J M, Ma J, Bai Y, Cao S, Zhang S T, Pang H. Adv. Colloid Interface Sci., 2022, 307: 102732.

[57]
Mageto T, de Souza F M, Kaur J, Kumar A, Gupta R K. Fuel Process. Technol., 2023, 242: 107659.

[58]
Wang M C, Dong R H, Feng X L. Chem. Soc. Rev., 2021, 50(4): 2764.

[59]
Reddy R C K, Lin X M, Zeb A, Su C Y. Electrochem. Energy Rev., 2022, 5(2): 312.

[60]
Gopalakrishnan M, Ganesan S, Nguyen M T, Yonezawa T, Praserthdam S, Pornprasertsuk R, Kheawhom S. Chem. Eng. J., 2023, 457: 141334.

[61]
Chen P, Shen J X, Wang T L, Dai M, Si C H, Xie J X, Li M, Cong X T, Sun X. J. Power Sources, 2018, 400: 325.

[62]
Chen P, Ren H M, Yan L T, Shen J X, Wang T L, Li G D, Chen S W, Cong X T, Xie J X, Li W. ACS Sustainable Chem. Eng., 2019, 7(19): 16612.

[63]
Lin G, Jia K, Bai Z X, Liu C C, Liu S N, Huang Y M, Liu X B. Adv. Funct. Mater., 2022, 32(47): 2207969.

[64]
Hao Z D, Wu Y, Zhao Q, Tang J D, Zhang Q Q, Ke X X, Liu J B, Jin Y H, Wang H. Adv. Funct. Mater., 2021, 31(33): 2102938.

[65]
Wang C J, Hao Z D, Hu Y T, Wu Y, Liu J B, Jin Y H, Wang H, Zhang Q Q. J. Mater. Chem. A, 2023, 11(15): 8131.

[66]
Zhang C, Shen L, Shen J Q, Liu F, Chen G, Tao R, Ma S X, Peng Y T, Lu Y F. Adv. Mater., 2019, 31(21): 1808338.

[67]
Bin Son H, Cho S, Baek K, Jung J, Nam S, Han D Y, Kang S J, Moon H R, Park S. Adv. Funct. Mater., 2023, 33(37): 2302563.

[68]
Liu W X, Huang X C, Meng Y, Xiao D, Guo Y. J. Mater. Chem. A, 2023, 11(25): 13446.

[69]
Shrivastav V, Sundriyal S, Goel P, Kaur H, Tuteja S K, Vikrant K, Kim K H, Tiwari U K, Deep A. Coord. Chem. Rev., 2019, 393: 48.

[70]
Sun X X, Li M C, Ren S X, Lei T Z, Lee S Y, Lee S, Wu Q L. J. Power Sources, 2020, 454: 227878.

[71]
Huang C H, Ji H, Yang Y, Guo B, Luo L, Meng Z H, Fan L L, Xu J. Carbohydr. Polym., 2020, 230: 115570.

[72]
Gwon H, Park K, Chung S C, Kim R H, Kang J K, Ji S M, Kim N J, Lee S, Ku J H, Do E C, Park S, Kim M, Shim W Y, Rhee H S, Kim J Y, Kim J, Kim T Y, Yamaguchi Y, Iwamuro R, Saito S, Kim G, Jung I S, Park H, Lee C, Lee S, Jeon W S, Jang W D, Kim H U, Lee S Y, Im D, Doo S G, Lee S Y, Lee H C, Park J H. Proc. Natl. Acad. Sci. U. S. A., 2019, 116(39): 19288.

[73]
Zhang S F, Luo J, Du M, Zhang F J, He X N. Cellulose, 2022, 29(9): 5163.

[74]
Huang Q M, Zhao C S, Li X. Cellulose, 2021, 28(5): 3097.

[75]
Zhang S F, Luo J, Zhang F J, Du M, Hui H Y, Zhao F X, He X N, Sun Z X. J. Membr. Sci., 2022, 652: 120461.

[76]
Ahmadi P, Nazeri N, Ali Derakhshan M, Ghanbari H. Int. J. Biol. Macromol., 2021, 180: 590.

[77]
Zhao J, Li Y, Sheng J L, Wang X F, Liu L F, Yu J Y, Ding B. ACS Appl. Mater. Interfaces, 2017, 9(34): 29302.

[78]
Deng L X, Wang Y Q, Cai C Y, Wei Z C, Fu Y. Carbohydr. Polym., 2021, 274: 118620.

[79]
Valverde A, Gonçalves R, Silva M M, Wuttke S, Fidalgo-Marijuan A, Costa C M, Vilas-Vilela J L, Laza J M, Arriortua M I, Lanceros-Méndez S, Fernández de Luis R. ACS Appl. Energy Mater., 2020, 3(12): 11907.

[80]
Liu X T, Wu Y N, Yang F, Wang S C, Zhang B, Wang L. J. Membr. Sci., 2021, 626: 119190.

[81]
Li M Y, Cheng S, Zhang J S, Huang C, Gu J P, Han J, Xu X, Chen X, Zhang P C, You Y. Chem. Eng. J., 2024, 487: 150709.

[82]
Liu J, Liu Y B, Yang W X, Ren Q, Li F Y, Huang Z. J. Power Sources, 2018, 396: 265.

[83]
Liu Y Z, Lv S, Zhang M Z, He J L, Ni P H. Colloids Surf. A Physicochem. Eng. Aspects, 2023, 667: 131359.

[84]
Hu J N, Liu Y Z, Zhang M Z, He J L, Ni P H. Electrochim. Acta, 2020, 334: 135585.

[85]
Xian D X, Liao Z X, Min Y, Wei G Y, Huang J Z, Zhang B, Wang L. Chem. Eng. J., 2023, 474: 145582.

[86]
Hou Y, Huang Z D, Chen Z, Li X L, Chen A, Li P, Wang Y B, Zhi C Y. Nano Energy, 2022, 97: 107204.

[87]
Lee D J, Yu X L, Sikma R E, Li M Q, Cohen S M, Cai G R, Chen Z. ACS Appl. Mater. Interfaces, 2022, 14(30): 34742.

[88]
Min Y, Liu X T, Guo L, Wu A G, Xian D X, Zhang B, Wang L. ACS Appl. Energy Mater., 2022, 5(7): 9131.

[89]
Li J Q, Chen L, Wang F L, Qin Z Y, Zhang Y, Zhang N, Liu X H, Chen G. Chem. Eng. J., 2023, 451: 138536.

[90]
Shi W Y, Shen J Q, Shen L, Hu W, Xu P C, Baucom J A, Ma S X, Yang S X, Chen X M, Lu Y F. Nano Lett., 2020, 20(7): 5435.

[91]
Shen M H, Ma H L. Coord. Chem. Rev., 2022, 470: 214715.

[92]
He Y B, Wu S C, Li Q, Zhou H S. Small, 2019, 15(47): 1904332.

[93]
Yang M, Nan J, Chen W, Hu A J, Sun H, Chen Y F, Wu C Y. Electrochem. Commun., 2021, 125: 106971.

[94]
Li W W, Yang B, Pang R X, Zhang M Y. Compos. Commun., 2023, 38: 101489.

[95]
Deng C, Wang Z W, Wang S P, Yu J X, Martin D J, Nanjundan A K, Yamauchi Y. ACS Appl. Mater. Interfaces, 2019, 11(1): 541.

[96]
Zhou H F, Tang Q L, Xu Q E, Zhang Y, Huang C, Xu Y L, Hu A P, Chen X H. RSC Adv., 2020, 10(31): 18115.

[97]
Zhu P, Zhu J D, Zang J, Chen C, Lu Y, Jiang M J, Yan C Y, Dirican M, Kalai Selvan R, Zhang X W. J. Mater. Chem. A, 2017, 5(29): 15096.

[98]
Guo P Q, Jiang P F, Chen W X, Qian G Y, He D Y, Lu X. Electrochim. Acta, 2022, 428: 140955.

[99]
Cheng Z B, Pan H, Chen J Q, Meng X P, Wang R H. Adv. Energy Mater., 2019, 9(32): 1901609.

[100]
Wang X, Yang L W, Li Q, Wang Y, Zhong Y J, Song Y, Chen Y X, Wu Z G, Zhong B H, Guo X D. Ind. Eng. Chem. Res., 2022, 61(4): 1761.

[101]
Zhu L, You L J, Zhu P H, Shen X Q, Yang L Z, Xiao K S. ACS Sustainable Chem. Eng., 2018, 6(1): 248.

[102]
Li Y P, Lei D, Jiang T Y, Guo J L, Deng X Y, Zhang X, Hao C, Zhang F X. Chem. Eng. J., 2021, 426: 131798.

[103]
Yang Y B, Wang S X, Zhang L T, Deng Y F, Xu H, Qin X S, Chen G H. Chem. Eng. J., 2019, 369: 77.

[104]
Yang H, Yang Y N, Zhang X, Li Y P, Qaisrani N A, Zhang F X, Hao C. ACS Appl. Mater. Interfaces, 2019, 11(35): 31860.

[105]
Ren J C, Huang Y L, Zhu H, Zhang B H, Zhu H K, Shen S H, Tan G Q, Wu F, He H, Lan S, Xia X H, Liu Q. Carbon Energy, 2020, 2(2): 176.

[106]
Bai S Y, Liu X Z, Zhu K, Wu S C, Zhou H S. Nat. Energy, 2016, 1(7): 16094.

[107]
Suriyakumar S, Kanagaraj M, Kathiresan M, Angulakshmi N, Thomas S, Stephan A M. Electrochim. Acta, 2018, 265: 151.

[108]
Qi C, Xu L, Wang J, Li H L, Zhao C C, Wang L N, Liu T X. ACS Sustainable Chem. Eng., 2020, 8(34): 12968.

[109]
Zang Y, Pei F, Huang J H, Fu Z H, Xu G, Fang X L. Adv. Energy Mater., 2018, 8(31): 1870136.

[110]
Fan Y P, Niu Z H, Zhang F, Zhang R, Zhao Y, Lu G. ACS Omega, 2019, 4(6): 10328.

[111]
Tian M, Pei F, Yao M S, Fu Z H, Lin L L, Wu G D, Xu G, Kitagawa H, Fang X L. Energy Storage Mater., 2019, 21: 14.

[112]
Dang B Y, Li Q Q, Luo Y H, Zhao R H, Li J D, Wu F C. J. Alloys Compd., 2022, 915: 165375.

[113]
Guo Y, Sun M H, Liang H Q, Ying W, Zeng X Q, Ying Y L, Zhou S D, Liang C D, Lin Z, Peng X S. ACS Appl. Mater. Interfaces, 2018, 10(36): 30451.

[114]
Diao W Y, Xie D, Li D L, Tao F Y, Liu C, Sun H Z, Zhang X Y, Li W L, Wu X L, Zhang J P. J. Colloid Interface Sci., 2022, 627: 730.

[115]
Wu F, Zhao S Y, Chen L, Lu Y, Su Y F, Jia Y N, Bao L Y, Wang J, Chen S, Chen R J. Energy Storage Mater., 2018, 14: 383.

[116]
Song C L, Li G H, Yang Y, Hong X J, Huang S, Zheng Q F, Si L P, Zhang M, Cai Y P. Chem. Eng. J., 2020, 381: 122701.

[117]
Li Y J, Lin S Y, Wang D D, Gao T T, Song J W, Zhou P, Xu Z K, Yang Z H, Xiao N, Guo S J. Adv. Mater., 2020, 32(8): 1906722.

[118]
Huang Y Z, Wang Y Q, Fu Y. Chem. Eng. J., 2023, 454: 140250.

[119]
Liu J W, Wang J N, Zhu L, Chen X, Ma Q Y, Wang L, Wang X, Yan W. Chem. Eng. J., 2021, 411: 128540.

[120]
Wang X B, Luo Y H, Wang H Y, Wu C C, Zhang Z S, Li J D. J. Electroanal. Chem., 2021, 897: 115564.

[121]
Yu Y, Li T Y, Zhang H Z, Luo Y, Zhang H M, Zhang J W, Yan J W, Li X F. Nano Energy, 2020, 71: 104596.

[122]
Li W J, Luan X J, Zhu X X, Sun J, Fan L L. J. Mater. Sci., 2022, 57(42): 19946.

[123]
Kiai M S, Ponnada S, Eroglu O, Mansoor M, Aslfattahi N, Nguyen V, Gadkari S, Sharma R K. Dalton Trans., 2024, 53(1): 82.

[124]
Li H H, Wang Y X, Chen H Q, Niu B X, Zhang W C, Wu D P. Chem. Eng. J., 2021, 406: 126802.

[125]
Qian X Y, Wang Y H, Jin L N, Cheng J, Chen J Y, Huang B B. J. Electroanal. Chem., 2022, 907: 116029.

[126]
Luo Y, Bai H, Li B, Song X, Zhao J, Xiao Y, Lei S, Cheng B. J. Alloys Compd., 2021, 879: 160368.

[127]
Hu X H, Huang T, Wang S P, Lin S J, Feng Z H, Chung L H, He J. Electrochim. Acta, 2021, 398: 139317.

[128]
Liu Y H, Li L X, Wen A Y, Cao F F, Ye H. Energy Storage Mater., 2023, 55: 652.

[129]
Deng N P, Wang L Y, Feng Y, Liu M, Li Q X, Wang G, Zhang L T, Kang W M, Cheng B W, Liu Y. Chem. Eng. J., 2020, 388: 124241.

[130]
Huang Q H, Zeb A, Xu Z H, Sahar S, Zhou J E, Lin X M, Wu Z Y, Reddy R C K, Xiao X, Hu L. Coord. Chem. Rev., 2023, 494: 215335.

[131]
Chu Z H, Gao X C, Wang C Y, Wang T Y, Wang G X. J. Mater. Chem. A, 2021, 9(12): 7301.

[132]
Zheng Y, Zheng S S, Xue H G, Pang H. J. Mater. Chem. A, 2019, 7(8): 3469.

[133]
Liang Z B, Zhao R, Qiu T J, Zou R Q, Xu Q. EnergyChem, 2019, 1(1): 100001.

[134]
Hong X J, Song C L, Yang Y, Tan H C, Li G H, Cai Y P, Wang H X. ACS Nano, 2019, 13(2): 1923.

[135]
Ma L B, Chen R P, Zhu G Y, Hu Y, Wang Y R, Chen T, Liu J, Jin Z. ACS Nano, 2017, 11(7): 7274.

[136]
Su Y C, Wang W S, Wang W K, Wang A B, Huang Y Q, Guan Y P. J. Electrochem. Soc., 2022, 169(3): 030528.

[137]
Guo S J, Xiao Y B, Wang J, Ouyang Y, Li X, Deng H Y, He W C, Zeng Q H, Zhang W, Zhang Q, Huang S M. Nano Res., 2021, 14(12): 4556.

[138]
Wang Z Q, Huang W Y, Hua J C, Wang Y D, Yi H C, Zhao W G, Zhao Q H, Jia H, Fei B, Pan F. Small Meth., 2020, 4(7): 2000082.

[139]
Lin S J, Dong J L, Chen R W, Zhang G Y, Huang T, Li J T, Zhou H J, Chung L H, Hu X H, He J. J. Alloys Compd., 2023, 965: 171389.

[140]
Zhao X L, Wu Q, Wu F C, Luo Y H, Li J D, Jia A Z. J. Electroanal. Chem., 2023, 939: 117474.

[141]
Zhang X M, Li G R, Zhang Y G, Luo D, Yu A P, Wang X, Chen Z W. Nano Energy, 2021, 86: 106094.

[142]
Cheng Z B, Lian J, Chen Y Y, Tang Y Y, Huang Y L, Zhang J D, Xiang S C, Zhang Z J. CCS Chem., 2024, 6(4): 988.

[143]
Li B H, Pan Y X, Luo B, Zao J, Xiao Y H, Lei S J, Cheng B C. Electrochim. Acta, 2020, 344: 135811.

[144]
Feng Y, Wang G, Wang L Y, Ju J G, Kang W M, Deng N P, Cheng B W. J. Alloys Compd., 2021, 851: 156859.

[145]
Jin L N, Chen J Y, Qian X Y, Cheng J, Hao Q Y, Zhang K. Colloids Surf. A Physicochem. Eng. Aspects, 2023, 657: 130443.

[146]
Li F, Qian X Y, Jin L N. ACS Sustainable Chem. Eng., 2021, 9(46): 15469.

[147]
He J R, Chen Y F, Manthiram A. Energy Environ. Sci., 2018, 11(9): 2560.

[148]
Fang X Z, Jiang Y, Zhang K L, Hu G, Hu W W. New J. Chem., 2021, 45(5): 2361.

[149]
Chuah C Y, Li W, Samarasinghe S A S C, Sethunga G S M D P, Bae T H. Microporous Mesoporous Mater., 2019, 290: 109680.

[150]
Li H T, Jin Q, Li D M, Huan X H, Liu Y M, Feng G L, Zhao J, Yang W, Wu Z G, Zhong B H, Guo X D, Wang B. ACS Appl. Mater. Interfaces, 2020, 12(20): 22971.

[151]
Peng H, Zhang T P, Shao W L, Liu S Y, Hu F Y. Appl. Surf. Sci., 2021, 569: 150935.

[152]
Hao Q Y, Qian X Y, Jin L N, Cheng J, Zhao S L, Chen J Y, Zhang K, Li B Z, Pang S L, Shen X Q. J. Alloys Compd., 2023, 967: 171605.

[153]
Yang J, Kang D W, Kim H, Hwang B, Lee J W. Chem. Eng. J., 2023, 451: 138909.

[154]
Li J J, Li X Y, Fan X, Tang T, Li M, Zeng Y P, Wang H, Wen J F, Xiao J R. Carbon, 2022, 188: 155.

[155]
Leng X L, Zeng J, Yang M D, Li C P, Prabhakar Vattikuti S V, Chen J L, Li S, Shim J, Guo T, Ko T J. J. Energy Chem., 2023, 82: 484.

[156]
Ren Y L, Zhai Q X, Wang B, Hu L B, Ma Y J, Dai Y M, Tang S C, Meng X K. Chem. Eng. J., 2022, 439: 135535.

[157]
Shi X F, Liu M, Gu T, Han J Q, Ren R P, Lv Y K, Ren J. J. Alloys Compd., 2023, 960: 170938.

[158]
Razaq R, Din M M U, Småbråten D R, Eyupoglu V, Janakiram S, Sunde T O, Allahgoli N, Rettenwander D, Deng L Y. Adv. Energy Mater., 2024, 14(3): 2302897.

[159]
Pang S R, Liu Y X, Zhang Z, Li Y X, Li C G, Shi Z, Feng S H. Microporous Mesoporous Mater., 2024, 365: 112892.

[160]
Zhao T J, Wu H Y, Wen X H, Zhang J, Tang H B, Deng Y J, Liao S J, Tian X L. Coord. Chem. Rev., 2022, 468: 214642.

[161]
Yang H J, Qiao Y, Chang Z, Deng H, He P, Zhou H S. Adv. Mater., 2020, 32(38): 2004240.

[162]
Kong L J, Cheng M R, Huang H, Pang J D, Liu S, Xu Y H, Bu X H. EnergyChem, 2022, 4(6): 100090.

[163]
Maeboonruan N, Lohitkarn J, Poochai C, Lomas T, Wisitsoraat A, Kheawhom S, Siwamogsatham S, Tuantranont A, Sriprachuabwong C. J. Sci. Adv. Mater. Devices, 2022, 7(3): 100467.

[164]
Song Y, Ruan P C, Mao C W, Chang Y X, Wang L, Dai L, Zhou P, Lu B G, Zhou J, He Z X. Nano Micro Lett., 2022, 14(1): 218.

[165]
Bruce P G, Freunberger S A, Hardwick L J, Tarascon J M. Nat. Mater., 2012, 11(1): 19.

[166]
Qiao Y, He Y B, Wu S C, Jiang K Z, Li X, Guo S H, He P, Zhou H S. ACS Energy Lett., 2018, 3(2): 463.

[167]
Deng H, Chang Z, Qiu F L, Qiao Y, Yang H J, He P, Zhou H S. Adv. Energy Mater., 2020, 10(12): 1903953.

[168]
Peng S S, Zhang L Y, Zhang C K, Ding Y, Guo X L, He G H, Yu G H. Adv. Energy Mater., 2018, 8(33): 1802533.

[169]
Yang X B, Zhao L, Goh K, Sui X L, Meng L H, Wang Z B. ChemistrySelect, 2019, 4(15): 4633.

[170]
Zhai S X, Lu Z R, Ai Y N, Liu X, Wang Q, Lin J, He S J, Tian M, Chen L. J. Membr. Sci., 2022, 645: 120214.

[171]
Bai S Y, Kim B, Kim C, Tamwattana O, Park H, Kim J, Lee D, Kang K. Nat. Nanotechnol., 2021, 16(1): 77.

[172]
He Y B, Qiao Y, Chang Z, Zhou H S. Energy Environ. Sci., 2019, 12(8): 2327.

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