A heatproof electrospun PES/PVDF composite membrane as an advanced separator for lithium-ion batteries

In the present paper, the physicochemical properties of a novel composite fibrous membrane, based on a mixture of poly(aryl ether sulfone) (PES) and poly(vinylidene fluoride) (PVDF), as separators for lithium-ion batteries are reported and discussed. Compared with the pure PVDF fibrous membrane, the introduction of PES can decrease the PVDF crystallinity while increasing the proportion of α-phase. Meanwhile, the initial thermal decomposition temperature is enhanced by 24°C. Heat shrinkage tests and thermomechanical analyzers indicate the composite membrane has significantly improved thermal-dimensional stability. The shrinkage rate of the composite membrane after heat-treated at 180°C for 2 hr is only 4.8%, which is far below the Celgard separator (82%) and the pure PVDF fibrous membrane (75%). The composite membrane with excellent wettability demonstrates a high ionic conductivity (1.69 × 10⁻³ S cm⁻¹) at room temperature as well as high electrolyte uptake (595%). The cells assembled with the composite membrane exhibit more stable cycle performance, capacity retention, and C-rate capability than that with polyolefin separator. These results suggest that PES/PVDF composite fibrous membrane is an effective separator for high-performance Lithium-ion batteries.     

Electrospun nanofiber polyacrylonitrile coated separators to suppress the shuttle effect for long-life lithium–sulfur battery

Polymeric coating on the separator with effective polysulfides diffusion inhibition can provide intimate contact between intermediate polysulfides and conductive layer of separator for high-energy lithium–sulfur (Li–S) batteries. Herein, polyacrylonitrile–poly(1,5-diaminoanthraquinone) (PAN/PDAAQ) and PAN-potassium functionalized graphene (PAN/K-FGF) nanofibers are synthesized via electrospinning method and act as effective separators for Li–S batteries to minimize polysulfides diffusion toward the anode. PAN/K-FGF coated separator shows capacity retention of 768 mAh g⁻¹ after 100 cycles at 1C. The capacity maintains at 419 mAh g⁻¹ after 500 cycles. PAN/PDAAQ nanofibers are coated on glass fiber separator functions as physical and chemical barrier for polysulfides diffusion. Therefore, the cell with PAN/PDAAQ coating on the separator demonstrates capacity retention of 881 mAh g⁻¹ after 100 cycles at 1C and small capacity decay rate of 0.11% per cycle resulted in 800 cycles at 1C. PAN/PDAAQ could define as an ideal separator material for Li–S batteries. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48606.     

Cellulose acetate-based separators prepared by a reversible acetylation process for high-performance lithium-ion batteries

Lithium-ion batteries (LIBs) are one of the most widely used technologies for various applications. However, polyolefin separators can hardly meet the needs of the development of LIBs due to the poor heat shrinkage and bad wettability with the electrolyte. Herein, a cellulose acetate (CA)-based separator is developed by blending with cellulose nanocrystals (CNCs) using a simple reversible acetylation process. This separator exhibits inherent thermal stability and improved ionic conductivity due to the finger-like and sponge-like porous structure. Moreover, the discharge capacity of the separator with a CNC loading of 3% remains at 132.9 mA h g⁻¹ when the rate reverts to 0.2 C and the capacity retention reaches 89.5% after 50 cycles. Therefore, the obtained CA-based separators can be a competitive candidate for high-performance LIBs and point the way to sustainable development.     

聚丙烯腈/聚酯无纺布微孔复合锂电隔膜的制备及性能

为了改善锂电隔膜的耐热性、电解液亲和性和机械性能,本文以聚丙烯腈为主要材料,采用相转化法制备了聚酯无纺布支撑的聚丙烯腈微孔复合锂电隔膜,对隔膜的理化性能（孔道结构、机械性能、电解液性能和耐热性）和电池性能（循环性能、倍率性能）进行系统研究。结果表明,复合隔膜具有均匀的微孔结构,平均孔径约为425nm,孔隙率为74%,拉伸强度为30MPa;电解液亲和性良好,吸液率为385%,接触角接近0°,锂离子电导率较市售隔膜显著提高,达到1.65mS/cm;在150℃、0.5h的热处理条件下,复合隔膜的热收缩率为0。鉴于良好的理化特性,该隔膜所装配的钴酸锂/锂金属电池表现出优异的循环容量和倍率容量保持性,如在0.2C倍率下,经历200次循环后电池的放电容量保持率为95.2%,在10C倍率下电池的放电容量为0.5C倍率下的58.3%。因此,相转化法制备的聚丙烯腈基微孔复合隔膜在锂离子电池中显示出较好的应用前景。     

Resin-silica composite nanoparticle grafted polyethylene membranes for lithium ion batteries

To avoid the peeling-off of ceramic nanoparticles (NPs) from polyolefin membranes usually occurred in commercially available ceramic NPs coated polyolefin separators for lithium batteries, we propose a simple one-pot in-situ reaction method to modify commercial polyethylene (PE) separators by surface grafting 3-Aminophenol/formaldehyde (AF)/silica (SiO₂) composite NPs. The AF/SiO₂ composite NPs form self-supporting connected pores on the modified layer of the separator surface, which ensures the transportation of Li⁺. Moreover, the PE@AF/SiO₂ separators has higher electrolyte wettability and compatibility than neat PE separators attributed to the plentiful polar functional groups in the AF/SiO₂ layer and AF/SiO₂ composite NPs, resulting in higher lithium ion transference number (= 0.62) and ionic conductivity (σ = 0.722 mS cm⁻¹). More importantly, the discharge capacity, capacity retention rate and coulombic efficiency (136.2 mA h g⁻¹, 87.9% and 99%, respectively) after 200 cycles of Li|NMC half batteries with PE@AF/SiO₂ separators, are all more excellent than that with the pure PE separator (125 mA h g⁻¹, 83.1% and 85%, respectively). Our results show that the PE@AF/SiO₂ separators obtained by this modification method have higher electrochemical stability in the lithium battery system.     

Electrospun Polyacrylonitrile/Polyvinylidene Fluoride/Boehmite Separator and Gel Polymer Electrolyte Polyethylene Oxide/Polyvinylidene Fluoride-hexafluoropropylene/Lithium Bis(trifluoromethanesulfonyl)imide/Boehmite Composite Separator Are Used for Fast Charging

With the increasing popularity of electric vehicles, the fast charging of lithium (Li) batteries is attracting increasing attention. However, the rapid decline in battery capacity caused by fast charging and accidents caused by Li dendrites piercing the separator greatly restrict fast-charging applications. Herein, an electrospun polyacrylonitrile/polyvinylidene fluoride/boehmite (PAN/PVDF/12 wt.% AlO(OH)) and gel polymer polyethylene oxide/polyvinylidene fluoride-hexafluoropropylene/lithium bis(trifluoromethanesulfonyl)imide/boehmite (PEO/PVDF-HFP/12.6 wt.% LiTFSI /10 wt.% AlO(OH)) pressed together to form a two-layer functional separator is designed. The electrospun separator improves the high-temperature resistance of the entire separator due to its special structure. After the 1 h heat treatment at 220 °C, the thermal shrinkage rate of the double-layer separator reaches 10.1%, showing good thermal stability. At 0.2 C, the discharge capacity retention rate is 99.4% after 100 cycles. After 1000 cycles at a rate of 10 C, the discharge capacity remains at 88% of the initial value. The two-layer separator exhibits better capacity retention and superior rate performance than PP, providing an effective approach for commercializing fast-charging functional separators.     

Electrochemical performance and thermal stability of the electrospun PTFE nanofiber separator for lithium‐ion batteries

Separator is a very important set of lithium‐ion batteries. At present, low porosity and poor thermal stability are two major disadvantages of separator. In this work, we first apply electrospinning method to prepare the Polytetrafluoroethylene (PTFE) nanofiber separator, which has the advantages of electrospinning method and PTFE materials. The effect of the PTFE nanofiber separator is investigated by scanning electron microscope, Capillary Flow Porometer, thermogravimetric–differential scanning calorimeter, linear sweep voltammeter, AC impedance, and charge/discharge cycling tests. The results demonstrate that the PTFE nanofiber separator has a special fiber structure made from PTFE particles gathering one by one along the fibers. Moreover, the PTFE nanofiber separator exhibits several advantages, including suitable pore diameter, uniform pore size distribution, high porosity, and electrolyte uptake, which enhance the ionic conductivity. The thermal stability of the PTFE nanofiber separator is much better than that of the conventional polyolefin separator. The Li/LiCoO₂ cell equipped with PTFE nanofiber separator exhibits excellent rate performance and first charge–discharge specific capacity of 142 and 131 mA h g^?1, respectively, accompanied by relatively stable cycle performance at 0.2 C rate. It is supposed to be a candidate for application in lithium‐ion batteries. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46508.     

PIN/PAN聚合物基电解质膜的制备及性能

利用静电纺丝技术制备了聚吲哚/聚丙烯腈(PIN/PAN)聚合物基电解质膜,代替纸基铝空气电池中的纤维素纸(C-P),并应用于固态铝空气电池。探究了PIN含量对电解质膜离子电导率及吸液率的影响。采用SEM和FTIR对PIN/PAN聚合物基电解质膜表面形貌及化学组成进行分析。借助电化学工作站和电池测试系统,分析了电解质膜离子电导率及固态铝空气电池放电特性。结果表明,采用PIN/PAN聚合物基电解质膜可有效提升固态铝空气电池性能,在3 mA.cm_^-2、5 mA.cm_^-2、7 mA.cm_^-2电流密度下,放电时长比纸基铝空气电池分别提升了21%、27%、34%,且放电时长与电解质膜的吸液率及离子电导率相关。其中4%PIN/PAN聚合物基电解质膜离子电导率可达6.7×10_^-4 S.cm_^-1,同时对碱性溶液具有良好的吸附能力,吸液率最高可达496%,为纤维素纸的3.2倍。     

Hierarchical self-assembly of tannic acid/diethylenetriamine on polypropylene for high-performance separator

In lithium-ion batteries (LIBs), separator is used to provide a barrier between the anode and cathode and provide freedom for the transport of lithium-ions, which serves a key function in inhibiting internal short circuit and improving the battery safety. The limited wettability of commercial polyolefin separators in electrolytes restricts its utilization in extreme environmental conditions. In our work, we choose polypropylene (PP) as the precursor and can address the issue of poor wettability through suitable modification methods. Tannic acid (TA) and diethylenetriamine (DETA) were utilized to coat PP separator via hierarchical self-assembly approach, and the coating is further stabilized by taking advantage of the specific oxidizing properties of sodium periodate. This method scarcely increases the separator thickness or sacrifices the microporous structure of the original separator. The improved separator not only exhibits outstanding wetting capability and relatively high ion conductivity (1.24 mS cm⁻¹), but also has the highest lithium-ion migration number of 0.74. This indicates that when the modified separator is applied to LIBs, its electrochemical performance is significantly enhanced. The enhancement in electrochemical performance of LIBs is attributed to the strong absorption and retention ability of the coating on the separator. The reversible capacity of Li/PP-TD2 separator/LiFePO₄ battery is 144.3 mAh g⁻¹ at 2C, which is higher than that of PP separator (117.1 mAh g⁻¹) under the same current density. Even after 200 cycles, the PP-TD2 separator with two-layer assembly modification still maintains a higher coulombic efficiency of 97.55% and a discharge capacity of 96.6%. This hierarchical self-assembly modification of PP provides an effective approach for fabricating high-performance separator.     

ForceSpinning of polyacrylonitrile for mass production of lithium‐ion battery separators

We present results on the Forcespinning^® (FS) of Polyacrylonitrile (PAN) for mass production of polymer nanofiber membranes as separators for Lithium‐ion batteries (LIBs). Our results presented here show that uniform, highly fibrous mats from PAN produced using Forcespinning^®, exhibit improved electrochemical properties such as electrolyte uptake, low interfacial resistance, high oxidation limit, high ionic conductivity, and good cycling performance when used in lithium ion batteries compared to commercial PP separator materials. This article introduces ForceSpinning^®, a cost effective technique capable of mass producing high quality fibrous mats, which is completely different technology than the commonly used in‐house centrifugal method. This Forcespinning^® technology is thus the beginning of the nano/micro fiber revolution in large scale production for battery separator application. This is the first time to report results on the cycle performance of LIB‐based polymer nanofiber separators made by Forcespinning^® technology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42847.     

PVDF/TiO2/graphene oxide composite nanofiber membranes serving as separators in lithium-ion batteries

Improving the electrochemical properties of membranes in lithium-ion batteries (LIBs) is very important. Many attempts have been made to optimize ionic conductivity of membranes. The aim of this study was fabricating composite nanofiber membranes of poly(vinylidene fluoride) (PVDF), containing titanium dioxide (TiO₂) and graphene oxide (GO) nanoparticles to use in LIBs as separators. The morphology, crystallinity, porosity, pore size, electrolyte uptake, ionic conductivity, and electrochemical stability of the membranes were investigated using scanning electron microscopy, wide-angle X-ray diffraction, Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, and linear sweep voltammetry. The electrolyte uptake and ionic conductivity of the PVDF/TiO₂/GO composite nanofiber membranes containing 2 wt % GO were 494% and 4.87 mS cm⁻¹, respectively, which were higher than those of the other fabricated membranes as well as the commercial Celgard membrane. This could be attributed to the increased porosity, larger surface area, and higher amorphous regions of the PVDF/TiO₂/GO composite nanofiber membranes as a result of the synergistic effects of the nanoparticles. In this work, suitable optimized membranes with greater electrochemical stability compared with the other membranes were presented. Also, it was demonstrated that the incorporation of the TiO₂ and GO nanoparticles into the PVDF nanofiber membranes led to a porous structure where the electrolyte uptake enhanced. These properties made these membranes promising candidates for being used as separators in LIBs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48775.     

The Enhanced Performance of Polyethylene Composite Separators by the Modification of Lithium Salt@SiO2 Nanoparticles

Improving the dimensional thermal stability and electrochemical performance of polyethylene (PE) membrane is critical to enhance the safety performance of lithium-ion battery. In this paper, PE membranes are modified by lithium bis(trifuoromethanesulfonyl)imide (LiTFSI) solution and then coated with nano-SiO₂/polyvinyl alcohol solution to obtain composite membranes (PE@LnSiO₂, where n represents the concentration of LiTFSI solution). The obtained PE@L4SiO₂ (LiTFSI solution concentration is 4%) composite membrane possesses a thermal shrinkage rate of only 17% at 150 °C, which is far superior to that of the PE separator. The ionic conductivity of the composite membrane is 16.9 × 10⁻⁴ S cm⁻¹ at room temperature (RT), and the battery impedance decreases to 154 Ω, which is remarkably better than that of the PE membrane (188 Ω). The battery delivers a reversible discharge capacity of 164 mAh g⁻¹ at 0.2 C under RT after 250 cycles, and the coulomb efficiency remains above 99%. The battery also has a high discharge capacity of 132 mAh g⁻¹ at 2 C, which indicates that it has excellent rate performance. Therefore, this research successfully explores a simple method to effectively improve the dimensional thermal stability of PE separator, as well as the electrochemical and safety performance of lithium battery.     

Electrochemical performance and thermal property of electrospun PPESK/PVDF/PPESK composite separator for lithium-ion battery

In this study, PPESK/PVDF/PPESK tri-layer composite separators for lithium-ion batteries were prepared by electrospinning technique. The physical properties, electrochemical performances and thermal properties of composite separators were investigated. Results indicate that PPESK/PVDF/PPESK separator displays good wettability in liquid electrolyte. The electrolyte uptake of PPESK/PVDF/PPESK separator is much higher than that of electrospun PVDF, which leads to higher ionic conductivity of PPESK/PVDF/PPESK separator than PVDF separator. Discharge capacity of the cell assembled with PPESK/PVDF/PPESK separator is increased by 50 % than that with PVDF separator. Initial charge–discharge efficiency and capacity retention property of the cell with PPESK/PVDF/PPESK are better than those with PVDF separator or PPESK separator. In addition, when the mass ratio between PPESK and PVDF resins is increased to 4:3, PPESK/PVDF/PPESK separators show good thermal dimensional stability even thermally treated at 180 °C for 1 h.     

A phase inversion based sponge-like polysulfonamide/SiO2 composite separator for high performance lithium-ion batteries

In this work,a sponge-like polysulfonamide(PSA)/SiO_2 composite membrane is unprecedentedly prepared by the phase inversion method,and successfully demonstrated as a novel separator of lithium-ion batteries(LIBs).Compared to the commercial polypropylene(PP) separator,the sponge-like PSA/SiO_2 composite possesses better physical and electrochemical properties,such as higher porosity,ionic conductivity,thermal stability and flame retarding ability.The LiCoO_2/Li half-cells using the sponge-like composite separator demonstrate superior rate capability and cyclability over those using the commercial PP separator.Moreover,the sponge-like composite separator can ensure the normal operation of LiCoO_2/Li half-cell at an extremely high temperature of 90 °C,while the commercial PP separator cannot.All these encouraging results suggest that this phase inversion based sponge-like PSA/SiO_2 composite separator is really a promising separator for high performance LIBs.     

Mass‐Production of Electrospun Carbon Nanofiber Containing SiOx for Lithium‐Ion Batteries with Enhanced Capacity

In this study, electrospun carbon nanofibers hybridized with silicon oxide (SiO_x) are prepared by using a syringeless electrospinning system of polyacrylonitrile (PAN) solution containing tetraethylorthosilicate (TEOS) via a sequential pyrolysis process. The syringeless electrospinning system provides a large number of composite nanofibers in a short time, and the obtained composite nanofibers exhibit uniform diameter and morphology. The composite nanofiber is converted into a carbon nanofiber containing SiO_x via a simple pyrolysis. The obtained SiO_x‐carbon nanofiber mat exhibits higher charge/discharge capacity than a general carbon nanofiber, and it provides more stable retention than single crystalline silicon materials. Thus, the mass‐production of a SiO_x‐carbon nanofiber from syringeless electrospinning is a promising method to produce anodic materials for Li‐ion batteries.     

Electrospun hydrophilic fumed silica/polyacrylonitrile nanofiber-based composite electrolyte membranes

Hydrophilic fumed silica (SiO₂)/polyacrylonitrile (PAN) composite electrolyte membranes were prepared by electrospinning composite solutions of SiO₂ and PAN in N,N-dimethylformamide (DMF). Among electrospinning solutions with various SiO₂ contents, the 12 wt% SiO₂ in PAN solution has highest zeta potential (−40.82 mV), and exhibits the best dispersibility of SiO₂ particles. The resultant 12 wt% SiO₂/PAN nanofiber membrane has the smallest average fiber diameter, highest porosity, and largest specific surface area. In addition, this membrane has a three-dimensional network structure, which is fully interconnected with combined mesopores and macropores because of a good SiO₂ dispersion. Composite electrolyte membranes were prepared by soaking these porous nanofiber membranes in 1 M lithium hexafluorophosphate (LiPF₆) in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 vol%). It is found that 12 wt% SiO₂/PAN electrolyte membrane has the highest conductivity (1.1 × 10⁻² S cm⁻¹) due to the large liquid electrolyte uptake (about 490%). In addition, the electrochemical performance of composite electrolyte membranes is also improved after the introduction of SiO₂. For initial cycle, 12 wt% SiO₂/PAN composite electrolyte membrane delivers the discharge capacity of 139 mAh g⁻¹ as 98% of theoretical value, and still retains a high value of 127 mAh g⁻¹ as 89% at 150th cycle, which is significantly higher that of pure PAN nanofiber-based electrolyte membranes.     

Fabrication and characterization of LATP/PAN composite fiber-based lithium-ion battery separators

Lithium aluminum titanium phosphate (LATP)/polyacrylonitrile (PAN) composite fiber-based membranes were prepared by electrospinning dispersions of LATP particles in PAN solutions. The electrolyte uptakes of the electrospun LATP/PAN composite fiber-based membranes were measured and the results showed that the electrolyte uptake increased as the LATP content increased. The lithium ion conductivity, the electrochemical oxidation limit and the interface resistance of liquid electrolyte-soaked electrospun LATP/PAN composite fiber-based membranes were also measured and it was found that as the LATP content increased, the electrospun LATP/PAN composite fiber-based membranes had higher lithium ion conductivity, better electrochemical stability, and lower interfacial resistance with lithium electrode. Additionally, lithium//1 M LiPF₆/EC/EMC//lithium iron phosphate cells using LATP/PAN composite fiber-based membranes as the separator demonstrated high charge/discharge capacity and good cycle performance.     

A poly(ethylene terephthalate) nonwoven sandwiched electrospun polysulfonamide fibrous separator for rechargeable lithium ion batteries

A poly(ethylene terephthalate) nonwoven sandwiched electrospun polysulfonamide (PSA) fibrous separator was developed for application in lithium‐ion batteries (LIBs). The poly(ethylene terephthalate) nonwoven served as a mechanical support and the PSA layers provided the separators with nanoporous structures. This novel composite separator possessed better thermal stability and electrolyte wettability than commercial polypropylene separator and the sandwiched nonwoven endowed the separator with an improved mechanical strength (17.7 MPa) compared to the pure electrospun PSA separator. The cells assembled with this composite separator displayed excellent discharge capacity (122.0 mAh g^?1 after 100 cycles) and discharge C‐rate capacity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44907.     

PAN/FPU Composite Nanofiber Membrane with Superhydrophobic and Superoleophobic Surface as a Filter Element for High-Efficiency Protective Masks

Recently, because of the outbreak of COVID-19, the demand for various types of filter elements in protective materials has increased globally. Furthermore, new requirements for the filtration performance of PM2.5 liquid (oil) particles have been put forward. In this work, Superhydrophobic and superoleophobic composite nanofibers with excellent filtration capacity for oil and salt particles are developed through the modification of polyacrylonitrile (PAN) by fluoro-polyurethane (FPU) doping. The results show that the PAN/FPU composite nanofibers doped with 9 wt% FPU has a uniform fiber morphology with a diameter of 240 ± 30 nm. Compared to the pure PAN nanofibers, the water-based contact angle of PAN/FPU increases from 90 ± 5° to 151 ± 5°, and the oil-based contact angle increases from 58 ± 2° to 152 ± 3°. Importantly, at a high flow rate of 95 L min⁻¹, the filtration efficiency of the PAN/FPU nanofiber membrane for 0.3 µm oil particles increases from 92 ± 1% to 99.2 ± 0.1%. After cyclic loading, the filtration efficiency of 0.3 µm oil particles remains above 98%. Meanwhile, the filtration efficiency for 0.3 µm salt particles remains at 98.23 ± 0.1%. The PAN/FPU nanofiber membrane developed in this work is effective in applications and has good market prospects as a protective filtration material.     

Reduced graphene oxide coated Fe-soc as a cathode material for high-performance lithium-sulfur batteries

To solve the problem of the rapid decrease in capacity caused by poor conductivity, polysulfide shuttling, and the volume expansion associated with the reaction process, we attempt to use metal-organic framework (MOF) Fe-soc coated with reduced graphene oxide through electrostatic adsorption as a sulfur carrier material for lithium sulfur batteries. The research results show that S/Fe-soc@rGO has a high initial discharge specific capacity of 1634.3 mA h g⁻¹ with a stable specific capacity retention rate of 865.3 mA h g⁻¹ after 80 cycles and displays enhanced rate performance with high discharge specific capacities of 638.8 and 334.3 mA h g⁻¹ after 200 cycles at 0.5 and 1 C, respectively. Fe-soc has unsaturated metal sites can adsorb sulfur and polysulfide, effectively bind polysulfide, symmetrical stable structure is conducive to speed up the electron and ion transmission efficiency while buffering the volume expansion during charge and discharge. In addition, reduced graphene oxide as a coating layer can better assist Fe-soc to increase the utilization rate of sulfur, and improve the conductivity of the cathode material, thereby improving the cycle performance and rate performance of lithium-sulfur batteries. This article is also expected to stimulate the application of MOF derivatives in energy storage materials.