A review of electrospun separators for lithium-based batteries: Progress and application prospects

Due to the limitations of the raw materials and processes involved,polyolefin separators used in commercial lithium-ion batteries(LIBs)have gradually failed to meet the increasing requirements of high-end batteries in terms of energy density,power density,and safety.Hence,it is very important to develop next-generation separators for advanced lithium(Li)-based recharge-able batteries including LIBs and Li-S batteries.Nonwoven nanofiber membranes fabricated via electrospinning technology are highly attractive candidates for high-end separators due to their simple processes,low-cost equipment,controllable microporous structure,wide material applicability,and availability of multiple functions.In this review,the electrospinning technologies for separators are reviewed in terms of devices,process and environment,and polymer solution systems.Furthermore,strategies toward the improvement of electrospun separators in advanced LIBs and Li-S batteries are presented in terms of the compositions and the structure of nanofibers and separators.Finally,the challenges and prospects of electrospun separators in both academia and industry are proposed.We anticipate that these systematic discussions can provide information in terms of commercial applications of electrospun separators and offer new perspectives for the design of functional electrospun separators for advanced Li-based batteries.

Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

Suppression of Self-Discharge in Aqueous Supercapacitor Devices Incorporating Highly Polar Nanofiber Separators

One of the major problems limiting the applications of electric double-layer(EDLC)supercapacitor devices is their inability to maintain their cell voltage over a significant period.Self-discharge is a spontaneous decay in charged energy,often resulting in fully depleted devices in a matter of hours.Here,a new method for suppressing this self-discharge phenomenon is proposed by using directionally polarized piezoelectric electrospun nanofiber films as separator materials.Tailored engineering of polyvinylidene fluoride(PVDF)nanofiber films containing a small concentration of sodium dodecyl sulfate(SDS)results in a high proportion of polarβphases,reaching 380.5%of the total material.Inducing polarity into the separator material provides a reverse-diode mechanism in the device,such that it drops from an initial voltage of 1.6 down to 1 V after 10 h,as opposed to 0.3 V with a nonpolarized,commercial separator material.Thus,the energy retained for the polarized separator is 37%and 4%for the nonpolarized separator,making supercapacitors a more attractive solution for long-term energy storage.

LiFePO_(4) as a dual-functional coating for separators in lithium-ion batteries:A new strategy for improving capacity and safety

Lithium-ion batteries(LIBs)require separators with high performance and safety to meet the increasing demands for energy storage applications.Coating electrochemically inert ceramic materials on conventional polyolefin separators can enhance stability but comes at the cost of increased weight and decreased capacity of the battery.Herein,a novel separator coated with lithium iron phosphate(LFP),an active cathode material,is developed via a simple and scalable process.The LFP-coated separator exhibits superior thermal stability,mechanical strength,electrolyte wettability,and ionic conductivity than the conventional polyethylene(PE)separator.Moreover,the LFP coating can actively participate in the electrochemical reaction during the charge-discharge process,thus enhancing the capacity of the battery.The results show that the LFP-coated separator can increase the cell capacity by 26%,and improve the rate capability by 29%at 4 C compared with the conventional PE separator.The LFP-coated separator exhibits only 1.1%thermal shrinkage at 140°C,a temperature even above the melting point of PE.This work introduces a new strategy for designing separators with dual functions for the next-generation LIBs with improved performance and safety.

Rational design and low-cost fabrication of multifunctional separators enabling high sulfur utilization in long-life lithium-sulfur batteries

The lithium-sulfur(Li-S)battery with an ultrahigh theoretical energy density has emerged as a promising rechargeable battery system.However,the practical applications of Li-S batteries are severely plagued by the sluggish reaction kinetics of sulfur species and notorious shuttling of soluble lithium polysulfides(LiPSs)intermediates that result in low sulfur utilization.The introduction of functional layers on separators has been considered as an effective strategy to improve the sulfur utilization in Li-S batteries by achieving effective regulation of LiPSs.Herein,a promising self-assembly strategy is proposed to achieve the low-cost fabrication of hollow and hierarchically porous Fe_(3)O_(4)nanospheres(p-Fe_(3)O_(4)-NSs)assembled by numerous extremely-small primary nanocrystals as building blocks.The rationally-designed p-Fe_(3)O_(4)-NSs are utilized as a multifunctional layer on the separator with highly efficient trapping and conversion features toward LiPSs.Results demonstrate that the nanostructured p-Fe_(3)O_(4)-NSs provide chemical adsorption toward LiPSs and kinetically promote the mutual transformation between LiPSs and Li_(2)S_(2)/Li_(2)S during cycling,thus inhibiting the LiPSs shuttling and boosting the redox reaction kinetics via a chemisorption-catalytic conversion mechanism.The enhanced wettability of the p-Fe_(3)O_(4)-NSs-based separator with the electrolyte enables fast transportation of lithium ions.Benefitting from these alluring properties,the functionalized separator with p-Fe_(3)O_(4)-NSs endows the battery with an admirable rate performance of 877 mAh g^(−1)at 2 C,an ultra-durable cycling performance of up to 2176 cycles at 1 C,and a promising areal capacity of 4.55 mAh cm^(−2)under high-sulfur-loading and lean-electrolyte conditions(4.29 mg cm^(−2),electrolyte/ratio:8μl mg^(−1)).This study will offer fresh insights on the rational design and low-cost fabrication of multifunctional separator to strengthen electrochemical reaction kinetics by regulating LiPSs conversion for developing efficient and long-life Li-S batteries.

An upgraded polymeric composite with interparticle chemical bonding microstructure toward lithium-ion battery separators with enhanced safety and electrochemical performances

A composite separator of SiC/PVDF-HFP was synthesized for lithium-ion batteries with high thermal and mechanical stabilities.Benefiting from the nanoscale,high hardness,and melting point of SiC,SiC/PVDFHFP with highly uniform microstructure was obtained.This polarization caused by barrier penetration was significantly restrained.Due to the Si-F bond between SiC and PVDF-HFP,the structural stability has been obviously enhanced,which could suppress the growth of lithium(Li) dendrite.Furthermore,some 3D reticulated Si nanowires are found on the surface of Li anode,which also greatly inhibit Li dendrites and result in irregular flakes of Li metal.Especially,the shrinkage of 6% SiC/PVDF-HFP at 150℃ is only 5%,which is notably lower than those of PVDF-HFP and Celgard2500.The commercial LiFePO_(4) cell assembled with 6% SiC/PVDF-HFP possesses a specific capacity of 157.8 mA h g^(-1) and coulomb efficiency of 98% at 80℃.In addition,the tensile strength and modulus of 6% SiC/PVDF-HFP could reach 14.6 and 562 MPa,respectively.And a small deformation(1000 nm) and strong deformation recovery are obtained under a high additional load(2.3 mN).Compared with PVDF-HFP and Celgard2500,the symmetric Li cell assembled with 6% SiC/PVDF-HFP has not polarized after 900 cycles due to its excellent mechanical stabilities.This strategy provides a feasible solution for the composite separator of high-safety batteries with a high temperature and impact resistance.

Thermal Stability and Electrochemical Properties of Separators for Lithium-ion Batteries

The mechanical properties,contact angle,thermomechanical and electrochemical properties of PE,PVDF,and ceramic separators were compared.The experimental results show that the PE separator has the largest porosity,the PVDF separator has the best mechanical properties,wettability,and heat resistance.Three kinds of separators were assembled into lithium-ion batteries for electrochemical tests.Among them,the PE separator has the best rate performance,and the ceramic separator has poor performance in charge-discharge cycles.At the same time,the PE and ceramic separators were tested with different amounts of electrolytes at room temperature and a high temperature,and it is found that the capacity of the PE separator is higher at room temperature,while the performance of the ceramic separator is better at a high temperature.The amount of electrolyte also has a certain influence on its electrochemical performance.

Research status and prospect of separators for magnesium-sulfur batteries

Magnesium-sulfur(Mg-S)batteries have attracted wide research attention in recent years,and are considered as one of the major candidates to replace lithium-ion batteries due to the high theoretical energy density,low costs of active materials,and high safety.However,there are still significant challenges that need to be overcome before they can reach the large-scale practical applications.The key issue is the dissolution and shuttle effect of magnesium polysulfides(Mg-PSs),which leads to severe capacity degradation and shortens cycling life,greatly limiting the development of Mg-S batteries.In order to overcome these challenges,great efforts have been made in cathode materials,electrolytes,and separators.Herein,we review the investigations on suppressing the shuttle effect of Mg-PSs via the modification of separators,including schemes such as coating the functional materials that can hold Mg-PSs on the surface of polyolefin-based or glass fiber(GF)separators,forming gel polymer separators via cross-linking polymerization reactions,and developing gel polymer electrolytes coupled with GF separators.Furthermore,an outlook is proposed for the future design on separator exploitation to accelerate the development of Mg-S battery technology.

Microporous Cyclodextrin Film with Funnel-type Channel Polymerized on Electrospun Cellulose Acetate Membrane as Separators for Strong Trapping Polysulfides and Boosting Charging in Lithium-Sulfur Batteries

The“shuttle effect”of polysulfides hampers the commercialization of lithium-sulfur(Li-S)batteries.Here,a thin molecular sieve film was decorated on the surface of an electrospun cellulose acetate(CA)membrane derived from recycled cigarette filters,where the truncated cone structureβ-cyclodextrin(β-CD)was selected as the building block to physically block and chemically trap polysulfides while simultaneously dramatically speeding up ion transport.Furthermore,on theβ-CD free side of the separator facing the cathode,graphite carbon(C)was sputtered as an upper current collector,which barely increases the thickness.These benefits result in an initial discharge performance of 1378.24 mAh g^(−1) and long-term cycling stability of 863.78 mAh g^(−1) after 1000 cycles at 0.2 C for the battery with theβ-CD/CA/C separator,which is more than three times that of the PP separator after 500 cycles.Surprisingly,the funnel-type channel ofβ-CD generates a differential ionic fluid pressure on both sides,speeding up ion transport by up to 69%,and a 65.3%faster charging rate of 9484 mA g^(−1) was achieved.The“funnel effect”of a separator is regarded as a novel and high-efficiency solution for fast charging of Li-S and other lithium secondary batteries.

Optimization of Control Loops and Operating Parameters for Three-Phase Separators Used in Oilfield Central Processing Facilities

In this study,the Stokes formula is used to analyze the separation effect of three-phase separators used in a Oilfield Central Processing Facility.The considered main influencing factors include(but are not limited to)the typical size of oil and water droplets,the residence time and temperature of fluid and the dosage of demulsifier.Using the“Specification for Oil and Gas Separators”as a basis,the control loops and operating parameters of each separator are optimized Considering the Halfaya Oilfield as a testbed,it is shown that the proposed approach can lead to good results in the production stage.

Metal-Organic Frameworks Functionalized Separators for Robust Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries(AZIBs)are one of the promising energy storage systems,which consist of electrode materials,electrolyte,and separator.The first two have been significantly received ample development,while the prominent role of the separators in manipulating the stability of the electrode has not attracted sufficient attention.In this work,a separator(UiO-66-GF)modified by Zr-based metal organic framework for robust AZIBs is proposed.UiO-66-GF effectively enhances the transport ability of charge carriers and demonstrates preferential orientation of(002)crystal plane,which is favorable for corrosion resistance and dendrite-free zinc deposition.Consequently,Zn|UiO-66-GF-2.2|Zn cells exhibit highly reversible plating/stripping behavior with long cycle life over 1650 h at 2.0 mA cm^(−2),and Zn|UiO-66-GF-2.2|MnO_(2) cells show excellent long-term stability with capacity retention of 85%after 1000 cycles.The reasonable design and application of multifunctional metal organic frameworks modified separators provide useful guidance for constructing durable AZIBs.

Polyimide separators for rechargeable batteries

Separators are indispensable components of modern electrochemical energy storage devices such as lithium-ion batteries(LIBs).They perform the critical function of physically separating the electrodes to prevent short-circuits while permitting the ions to pass through.While conventional separators using polypropylene(PP) and polyethylene(PE) are prone to shrinkage and melting at relatively high temperatures(150℃ or above) causing short circuits and thermal runaway,separators made of thermally stable polyimides(PIs) are electrochemically stable and resistant to high temperatures,and possess good mechanical strength-making them a promising solution to the safety concerns of LIBs.In this review,the research progress on PI separators for use in LIBs is summarized with a special focus on molecular design and microstructural control.In view of the significant progress in advanced chemistries beyond LIBs,recent advances in PI-based membranes for applications in lithium-sulfur,lithium-metal,and solid-state batteries are also reviewed.Finally,practical issues are also discussed along with their prospects.

Efficiency of Plate Separators for Dispersed Liquid-Liquid Systems

The basic flow model of laminar flow field and the trajectory model of dispersed phase drops are derived. Based on the comparable volumetric flow rate, the dispersed flow rate can be linearly discretized. Consequently, the trajectory of a droplet in the channel can be tracked, and the trajectories of all drops are observed in order to statistically analyse the drops for capture or entrainment. Therefore, in terms of theoretical model of motion, the stratified two phase flow systems are studied in the mixture of nitrobenzene and concentrated sulfuric acid. The analytical results indicate that the trajectories of droplets of different diameters are different at the same location. The larger droplets can help to promote the efficiency of plate separators. The thickness of trickling film has a significant influence on the efficiency of numerical simulation when the concentration of the dispersed phase is greater than 10%. So the modification of thickness of trickling film can help to get the real flow field efficiency. The low flow rate lowers the average Renolds number so that the lighter phase droplets have sufficient time to interact with the trickling film. It is an indispensable factor for predicting efficiency that coalesced drops flow off inclined plates together with trickling films. A comparison confirms that the simulation results are in good agreement with the experiment results.

Comparative study of different membranes as separators for rechargeable lithium-ion batteries

Membranes of polypropylene （PP）, PP coated with nano-A1203, PP electrospun with polyvinylidene fluoride- hexafluoropropylene （PVdF-HFP）, and trilayer laminates of polypropylene-polyethylene-polypropylene （PP/PE/PP） were comparatively studied. Their physical properties were characterized by means of thermal shrinkage test, liquid electrolyte uptake, and field emission scanning electron microscopy （FESEM）. Results show that, for the different membranes as PP, PP coated with nanowA1203, PP electrospun with PVdF-HFP, and PP/PE/PP, the thermal shrinkages are 14%, 6%, 12.6%, and 13.3%, while the liquid electrolyte uptakes are 110%, 150%, 217%, and 129%, respectively. In addition, the effects on the performance of lithium-ion batteries （LiFePO4 and LiNil/3Col/3Mn1/302 as the cathode material） were investigated by AC impedance and galvanostatic charge/discharge test. It is found that PP coated with A1203 and PP electrospun with PVdF-HFP can effectively increase the wettability between the cathode material and liquid electrolyte, and therefore reduce the charge transfer resistance, which improves the capacity retention and battery performance.

Automatic Control System for Magnetic Separators Based on PLC

To make magnetic separator more excellent in beneficiation, an advanced automatic control system for magnetic separator was designed. This paper designs automatic control system for magnetic separators, combination with PLC and technology of vary frequency. This system can wholly supervise and control the parameters of work course of magnetic separators.

Rational design on separators and liquid electrolytes for safer lithium-ion batteries

As the energy density of lithium-ion batteries (LIBs) continues to increase,their safety has become a great concern for further practical large-scale applications.One of the ultimate solution of the safety issue is to develop intrinsically safe battery components,where the battery separators and liquid electrolytes are critical for the battery thermal runaway process.In this review,we summarize recent progress in the rational materials design on battery separators and liquid electrolyte towards the goal of improving the safety of LIBs.Also,some strategies for further improving safety of LIBs are also briefly outlooked.

Numerical Study of Steam-Water Separators with Wave-type Vanes

Droplet behavior in the wave-type flow channel is discussed, especially with the secondary .droplet generation due to impingement of droplets on the wall considered. A numerical method is suggested to simulate tile droplet behavior in the flow field. Calculations are compared With experimental data on the ; pressure drop and separating efficiency. Good agreement exists between the calculations and air-water experiments. The numerical method developed gives a reasonable description of the droplet deposition and secondary droplet generation, and it can be applied to predict the performance of wave-type vane separators.

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is im- portant for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 ℃ for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.

Radiation graft of acrylamide onto polyethylene separators for lithium-ion batteries

To improve the affinity between separators and electrolyte in lithium-ion battery,microporous polyethylene(PE) separator was grafted of polyacrylamide(PAAm) by radiation.Chemical structure of the PAAmgrafted PE separators(denoted as PE-g-PAAm) was characterized by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Properties of the pristine PE and PE-g-PAAm were tested by scanning electron microscope,liquid electrolyte uptake and lithium-ion conductivity.Electrochemical performances of the grafted PE separators(up to 0.76 × 10^(-3) S/cm of ionic conductivity at room temperature) were much better than pristine PE,and performance of the battery with the grafted separator behaved better than with the virgin PE separator,under the same condition(assembled in Ar-filled glove box).

Dendrite-free lithium anode achieved under lean-electrolyte condition through the modification of separators with F-functionalized Ti_(3)C_(2)nanosheets

An unstable solid electrolyte interphase(SEI)and chaotic lithium ion fux are key impediments to commercial high-energy-density lithium batteries because of the uncontrolled growth of rigid lithium dendrites,which would pierce through the conventional polypropylene(PP)separator,causing short circuit and safety issues.Herein,the homogenization of lithium ion fux and the generation of stable SEI layers on lithium anodes were achieved via coating a fuorine-functionalized Ti_(3)C_(2)(F-Ti_(3)C_(2))nanosheets on PP separator(F-Ti_(3)C_(2)@PP).F-Ti_(3)C_(2)nanosheets provide abundant ions pathways to homogeneously manipulate lithium ion fux and increase the Young’s modulus and electrolyte wettability of the separators.In addition,F species derived from the F-Ti_(3)C_(2)nanosheets would promote the formation of Li F-rich SEI film.The synergistic effect contribute to the uniform lithium deposition.Symmetric Li|Li,asymmetric Li|Cu and full Li|Li Fe PO4cells incorporated with the modified separators exhibit improved electrochemical performance even under lean electrolyte conditions.This work provides a feasible strategy to improve the performance of lithium batteries through both fuoridized SEI formation and lithium ion fux manipulation.