Separator technologies for lithium-ion batteries

Although separators do not participate in the electrochemical reactions in a lithium-ion (Li-ion) battery, they perform the critical functions of physically separating the positive and negative electrodes while permitting the free flow of lithium ions through the liquid electrolyte that fill in their open porous structure. Separators for liquid electrolyte Li-ion batteries can be classified into porous polymeric membranes, nonwoven mats, and composite separators. Porous membranes are most commonly used due to their relatively low processing cost and good mechanical properties. Although not widely used in Li-ion batteries, nonwoven mats have the potential for low cost and thermally stable separators. Recent composite separators have attracted much attention, however, as they offer excellent thermal stability and wettability by the nonaqueous electrolyte. The present paper (1) presents an overview of separator characterization techniques, (2) reviews existing technologies for producing different types of separators, and (3) discusses directions for future investigation. Research into separator fabrication techniques and chemical modifications, coupled with the numerical modeling, should lead to further improvements in the performance and abuse tolerance as well as cost reduction of Li-ion batteries.     

Effect of silica nanoparticles/poly（vinylidene fluoride-hexafluoropropylene） coated layers on the performance of polypropylene separator for lithium-ion batteries

In an effort to reduce thermal shrinkage and improve electrochemical performance of porous polypropylene （PP） separators for lithium-ion batteries, a new composite separator is developed by introducing ceramic coated layers on both sides of PP separator through a dip-coating process. The coated layers are comprised of heat-resistant and hydrophilic silica nanoparticles and polyvinylidene fluoride-hexafluoropropylene （PVDF-HFP） binders. Highly porous honeycomb structure is formed and the thickness of the layer is only about 700 nm. In comparison to the pristine PP separator, the composite separator shows significant reduction in thermal shrinkage and improvement in liquid electrolyte uptake and ionic conduction, which play an important role in improving cell performance such as discharge capacity, C-rate capability, cycle performance and coulombic efficiency.     

锂离子电池凝胶聚合物隔膜的研究进展

作为锂离子电池重要组分,隔膜由多孔聚烯烃高分子材料组成;电解质体系由有机碳酸酯和六氟磷酸锂混合组成,虽具有高离子电导率,但因液态碳酸酯的易燃特性给锂离子电池带来了安全隐患。利用能够将液态电解质体系凝胶化的聚合物制备得到的凝胶聚合物隔膜,结合了液态电解质体系高电导率和固态电解质高安全性的优点。凝胶聚合物隔膜的研究从简单微孔凝胶聚合物隔膜开始,经历了引入少量纳米无机颗粒的掺杂凝胶聚合物隔膜,到引入大量纳米颗粒的凝胶陶瓷隔膜的发展历程。本文详细介绍这三种类型凝胶聚合物隔膜的物理化学特性,最后展望凝胶聚合物隔膜的发展趋势。     

Lithium-ion battery separators: Recent developments and state of art

Lithium-ion battery separators are receiving increased consideration from the scientific community. Single-layer and multilayer separators are well-established technologies, and the materials used span from polyolefins to blends and composites of fluorinated polymers. The addition of ceramic nanoparticles and separator coatings improves thermal and mechanical properties, as well as electrolyte uptake and ionic conductivity. The state-of-art separators are actively involved in the cell chemistry through specific functional groups on their surface. Among the numerous properties, safety features and long cycle life are high-priority requirements for next-generation lithium-ion batteries.     

Recent Development of Polyolefin‐Based Microporous Separators for Li−Ion Batteries: A Review

Secondary Li?ion batteries have been paid attention to wide‐range applications of power source for the portable electronics, electric vehicle, and electric storage reservoir. Generally, lithium‐ion batteries are comprised of four components including anode, cathode, electrolyte and separator. Although separators do not take part in the electrochemical reactions in a lithium‐ion (Li?ion) battery, they conduct the critical functions of physically separating the positive and negative electrodes to prevent electrical short circuit while permitting the free flow of lithium ions through the liquid electrolyte that fill in their open porous structure. Hence, the separator is directly related to the safety and the power performance of the battery. Among a number of separators developed thus far, polyethylene (PE) and polypropylene (PP) porous membrane separators have been the most dominant ones for commercial Li?ion batteries over the decades because of their superior properties such as cost‐efficiency, good mechanical strength and pore structure, electrochemical stability, and thermal shutdown properties. However, there are main issues for vehicular storage, such as nonpolarity, low surface energy and poor thermal stability, although the polyolefin separators have proven dependable in portable applications. Hence, in this review, we decide to provide an overview of the types of polyolefin microporous separators utilized in Li?ion batteries and the methods employed to modify their surface in detail. The remarkable results demonstrate that extraordinary properties can be exhibited by mono‐ and multilayer polyolefin separators if they are modified using suitable methods and materials.     

Cellular porous polyvinylidene fluoride composite membranes for lithium-ion batteries

Macroporous polyvinylidene fluoride (PVdF) membranes were prepared by a phase inversion method and evaluated as battery separators. Two totally different morphologies (cellular and finger-like) were obtained by coagulating PVdF solutions with two different solvents. The cellular membranes were formed immediately by precipitating the PVdF solution with a latent solvent (acetone) in water, while the finger-like membranes were precipitated from the PVdF solution with a true solvent (N-methyl-2-pyrrolidone). The incorporation of a silica filler decreased the ionic resistance of the PVdF membranes of both morphologies. However, the cellular membranes showed better mechanical properties and enabled higher ionic conductivities than the finger-like ones, especially when the silica loading was low. Compared with a conventional untreated polyolefin separator, the porous PVdF membranes showed good wettability by a liquid electrolyte. After being activated with a commercial LiPF₆–ethylene carbonate–dimethyl carbonate electrolyte, the PVdF membranes were tested for their applications in lithium-ion batteries. Coin cells with these PVdF membranes exhibited stable cycling performance and good rate capability at room temperature. However, the cellular membranes are preferred over the finger-like ones because they offer higher mechanical performance, and can be processed into flat membranes more easily.     

锂离子电池隔膜的功能化改性及表征技术

随着锂离子电池在动力和规模化储能等新能源领域应用的不断拓展,具有特殊功能且满足特定使用需求隔膜的设计准则、制备/改性方法及表征技术亟需系统深入研究。针对锂离子电池高性能和高安全性的要求,研究人员已通过结构设计和表面化学改性等策略优化了隔膜的本征特性,并通过系列表征技术探讨了隔膜的功能化改性对锂离子电池电化学性能的影响。基于以上背景,本文从离子传输、枝晶形核与生长、及安全性能三个方面详细探讨了隔膜对电池性能影响的关键因素及其改性方法,并系统总结了隔膜结构、物化特性、力学性能、热学性能以及电化学性能的表征技术,以期为功能隔膜的合理设计,从而优化锂离子电池性能提供理论和实践指导。同时,本文对隔膜未来的进一步研究和发展提出了展望。     

Polymer/colloid dual-phase electrolyte membrane for rechargeable lithium batteries

In this work, a polymer/ceramic phase-separation porous membrane is first prepared from polyvinyl alcohol–polyacrylonitrile water emulsion mixed with fumed nano-SiO₂ particles by the phase inversion method. This porous membrane is then wetted by a non-aqueous Li–salt liquid electrolyte to form the polymer/colloid dual-phase electrolyte membrane. Compared to the liquid electrolyte in conventional polyolefin separator, the obtained electrolyte membrane has superior properties in high ionic conductivity (1.9 mS?cm^?1 at 30 °C), high Li⁺ transference number (0.41), high electrochemical stability (extended up to 5.0 V versus Li⁺/Li on stainless steel electrode), and good interfacial stability with lithium metal. The test cell of Li/LiCoO₂ with the electrolyte membrane as separator also shows high-rate capability and excellent cycle performance. The polymer/colloid dual-phase electrolyte membrane shows promise for application in rechargeable lithium batteries.     

Improving the properties of HDPE based separators for lithium ion batteries by blending block with copolymer PE-b-PEG

To improve the performances of HDPE-based separators, polyether chains were incorporated into HDPE membranes by blending with poly(ethylene-block-ethylene glycol) (PE-b-PEG) via thermally induced phase separation (TIPS) process. By measuring the composition, morphology, crystallinity, ion conductivity, etc, the influence of PE-b-PEG on structures and properties of the blend separator were investigated. It was found that the incorporated PEG chains yielded higher surface energy for HDPE separator and improved affinity to liquid electrolyte. Thus, the stability of liquid electrolyte trapped in separator was increased while the interfacial resistance between separator and electrode was reduced effectively. The ionic conductivity of liquid electrolyte soaked separator could reach 1.28 × 10-3 S.cm-1 at 25℃, and the electrochemical stability window was up to 4.5 V (versus Li + /Li). These results revealed that blending PE-b-PEG into porous HDPE membranes could efficiently improve the performances of PE separators for lithium batteries.     

Evaluation of the main processing parameters influencing the performance of poly(vinylidene fluoride–trifluoroethylene) lithium-ion battery separators

Poly(vinylidene fluoride–trifluoroethylene) (PVDF–TrFE) membranes are evaluated for lithium-ion battery separator applications. Some of the main parameters affecting separator performance such as porosity, dehydration of lithium ions, and processing technique (Li-ion uptake versus composite formation) are investigated. The polymer characteristics, as determined by infrared spectroscopy, do not change as a function of porosity, dehydration of lithium ions in the electrolyte solution, or processing technique. The electrochemical impedance spectroscopy represented through the Nyquist plot, Bode plot, and the ionic conductivity as a function of temperature strongly depends on the aforementioned parameters. The membrane that exhibits the highest ionic conductivity is a porous membrane without dehydration of lithium ions and prepared by the uptake technique. The performance of the membrane for battery applications are, therefore, strongly influenced both by porosity and processing technique.     

锂离子电池用陶瓷聚烯烃复合隔膜

为改善聚烯烃微孔膜的耐热安全性,研究了用于锂离子电池的陶瓷聚烯烃复合隔膜ZrO2/SiO2/PP（聚丙烯）。 复合膜具有高度多孔性和良好液体电解液湿润性。 由于高的毛细吸附作用,通过吸附液态电解液,膜很易传导锂离子。 膜中ZrO2/SiO2的两性特征,将电解液中的酸性HF（氟化氢）消耗掉,而HF作为现在锂离子电池所用电解液中的杂质是不可避免的。 复合膜作为隔膜制备的碳/正极材料锂离子电池不仅具有优良的容量保持性、高温安全性,也显示良好的倍率放电性。     

Recent advances on battery separators based on poly(vinylidene fluoride) and its copolymers for lithium-ion battery applications

Lithium-ion batteries represent one of the most suitable systems for effective energy storage for a wide range of applications, such as smartphones, laptops, electric vehicles, or even home storage systems. Among the different battery components, the separator plays an essential role in the performance of the batteries; its most relevant characteristics are (micro)structure, wettability, thermal and mechanical properties, and ionic conductivity value. This work provides a comprehensive review of the current state of the art in lithium-ion battery separator membranes based on poly(vinylidene fluoride) (PVDF) and its copolymers. The most recent developments in the last two years are presented, focusing on the different separator types that have been developed with the aim of improving wettability, thermal characteristics, and cycling behavior. The most used types of PVDF separators are composites, polymer blends, and the combination of both. Among the most common fillers, metal–organic frameworks, ionic liquids, and ceramic particles have been used for the development of PVDF-based composites and polymers such as poly(m-phenylene isophthalamide), poly(acrylonitrile), poly(tetrafluoroethylene), or poly(methyl methacrylate), for the development of polymer blends. Electrospinning is one of the most used processing techniques to improve wettability, thermal stability, and mechanical properties. The wettability of separators has been also improved by using PVDF as a coating on commercial separators.It is shown that PVDF-based battery separators can play an important role in the next generation of high-performance batteries.     

Thickness difference induced pore structure variations in cellulosic separators for lithium-ion batteries

The pore structure of the separator is crucial to the performance of a lithium-battery as it affects the cell resistance. Herein, a straightforward approach to vary the pore structure of Cladophora cellulose (CC) separators is presented. It is demonstrated that the pore size and porosity of the CC separator can be increased merely by decreasing the thickness of the CC separator by using less CC in the manufacturing of the separator. As the pore size and porosity of the CC separator are increased, the mass transport through the separator is increased which decreases the electrolyte resistance in the pores of the separator. This enhances the battery performance, particularly at higher cycling rates, as is demonstrated for LiFePO₄/Li half-cells. A specific capacity of around 100 mAh g^?1 was hence obtained at a cycling rate of 2 C with a 10 µm thick CC separator while specific capacities of 40 and close to 0 mAh g^?1 were obtained for separators with thicknesses of 20 and 40 µm, respectively. As the results also showed that a higher ionic conductivity was obtained for the 10 µm thick CC separator than for the 20 and 40 µm thick CC separators, it is clear that the different pore structure of the separators was an important factor affecting the battery performance in addition to the separator thickness. The present straightforward, yet efficient, strategy for altering the pore structure hence holds significant promise for the manufacturing of separators with improved performance, as well as for fundamental studies of the influence of the properties of the separator on the performance of lithium-ion cells.     

纤维素微孔锂电隔膜的制备及性能研究

为了改善锂电隔膜的亲液性和耐高温性,以醋酸纤维素为成膜材料,利用相转化法制备了新型锂电隔膜,通过形貌和孔道结构表征、亲液性能和耐热性能测试对醋酸纤维素隔膜的基本性能进行研究,并将该隔膜装配成锂离子电池进行充放电性能测试. 结果表明,醋酸纤维素隔膜具有均匀的微孔结构,孔隙率达到65%,约为传统聚烯烃隔膜的1.5倍;纤维素材料的良好亲液性和高孔隙率结构改善了隔膜的吸液性能,其吸液率达到285%;该隔膜在150 ^oC、30 min的热处理条件下未发生明显的热收缩. 鉴于上述优点,相对于市售PE隔膜,醋酸纤维素隔膜所装配锂离子电池显示出更优的循环性能和倍率性能.     

Fabrication and characterization of P(VDF-HFP)/SBA-15 composite membranes for Li-ion batteries

This study reports on the preparation of a composite polymer electrolyte for secondary lithium-ion battery. Poly(vinylidiene fluoride-hexafluoropropylene) (P(VDF-HFP)) was used as the polymer host, and mesoporous SBA-15 (silica) ceramic fillers used as the solid plasticizer were added into the polymer matrix. The SBA-15 fillers with mesoporous structure and high specific surface can trap more liquid electrolytes to enhance the ionic conductivity. The ionic conductivity of P(VDF-HFP)/SBA-15 composite polymer electrolytes was in the order of 10⁻³ S cm⁻¹ at room temperature. The characteristic properties of the composite polymer membranes were examined by using FTIR spectroscopies, scanning electron microscopy (SEM), and an AC impedance method. For comparison, the LiFePO₄/Li composite batteries with a conventional microporous polyethylene (PE) separator and pure P(VDF-HFP) polymer membrane were also prepared and studied. As a result, the LiFePO₄/Li composite battery comprised the P(VDF-HFP)/10 wt.% m-SBA-15 composite polymer electrolyte, which achieves an optimal discharge capacity of 88 mAh g⁻¹ at 20 C rate with a high coulomb efficiency of 95%. It is demonstrated that the P(VDF-HFP)/m-SBA-15 composite membrane exhibits as a good candidate for application to LiFePO₄ polymer batteries.     

PVDF-HFP/PMMA-coated PE separator for lithium ion battery

Microporous poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP)/poly(methyl methacryate) (PMMA)-coated polyethylene (PE) separators were prepared by a simple dip-coating process with various compositions of PVDF-HFP/PMMA mixture under 40% relative humidity condition. The results indicate that the porosity, liquid electrolyte uptake, and ionic conductivity of the coated separators are largely affected by a ratio of PVDF-HFP/PMMA mixture and the highest porosity, electrolyte uptake, and ionic conductivity can be achieved at a composition of PVDF-HFP/PMMA (5/5). The results of the cell performance tests also reveal that the PE separator coated with PVDF-HFP/PMMA in a ratio of 5:5 provides better rate capability and cycle stability than other PE separators coated with different ratios.     

锂电隔膜研究及产业技术进展

隔膜是锂离子电池的关键材料,在极片间起绝缘和提供离子通道的作用.本文以如何构建耐高温的隔膜、如何提高隔膜的离子电导率为重点,介绍了锂电隔膜研究及产业化技术进展,内容主要包括隔膜性能的影响因素、凝胶聚合物电解质膜、拉伸法制备隔膜及其改性、隔膜制造的新方法和新材料.最后展望了隔膜的发展前景.     

Construction of PMIA@PAN/PVDF-HFP/TiO2 coaxial fibrous separator with enhanced mechanical strength and electrolyte affinity for lithium-ion batteries

Poly(m-phthaloyl-m-phenylenediamine) (PMIA) is promising as the separator in lithium-ion batteries (LIBs) for its excellent thermostability, insulation and self-extinguishing properties. However, its low mechanical strength and poor electrolyte affinity limit its application in LIBs. In this work, a new PMIA@polyacrylonitrile-polyvinylidene fluoride hexafluoropropylene-titanium dioxide (PMIA@PAN/PVDF-HFP/TiO₂) composite fibrous separator with a coaxial core-shell structure was developed by combining coaxial electrospinning, hot pressing, and heat treatment techniques. This separator not only inherits the exceptional thermostability of PMIA, showing no evident thermal shrinkage at 220 °C, but also reveals improved mechanical strength (29.7 MPa) due to the formation of firm connections between fibers with the melted PVDF-HFP. Meanwhile, the massive polar groups in PVDF-HFP play a vital role in improving the electrolyte affinity, which renders the separator a high ionic conductivity of 1.36 × 10⁻³ S/cm. Therefore, the LIBs with PMIA@PAN/PVDF-HFP/TiO₂ separators exhibited excellent cycling and rate performance at 25 °C, and a high capacity retention rate (76.2%) at 80 °C for 200 cycles at 1 C. Besides, the lithium metal symmetric battery assembled by the separator showed a small overpotential, indicating that the separator had a role in inhibiting lithium dendrites. In short, the PMIA@PAN/PVDF-HFP/TiO₂ separator possesses a wide application prospect in the domain of LIBs.     

Porous Membranes of Montmorillonite/Poly(vinylidene fluoride‐trifluorethylene) for Li‐Ion Battery Separators

Porous membranes of poly(vinylidene fluoride‐trifluoroethylene) with different contents of montmorillonite (MMT) particles were prepared. The filler content does not affect the porous morphology but leads to an increase in the average pore size, porosity and electrolyte uptake up to 16 μm, 85 % and 325 %, respectively, for a membrane with 16 wt% of MMT particles. The mechanical properties, ionic conductivity and its temperature stability are improved by the presence of clays. The electrochemical stability reveals a stable operation window up to 5 V. The overall characteristics of the membranes for battery separators are optimized for the 4 wt% MMT filler content.     

Composite gel membranes: a new class of improved polymer electrolytes for lithium batteries

Novel composite, gel-type polymer electrolytes have been prepared by dispersing selected ceramic powders into a matrix formed by a lithium salt solution contained in a poly(acrylonitrile) (PAN) network. The electrochemical characterization demonstrates that these new types of composite gel electrolytes have high ionic conductivity, wide electrochemical stability and, particularly, high chemical integrity (no liquid leakage) even at temperatures above ambient. These unique properties make the composite gel membranes particularly suitable as electrolyte separators in lithium ion polymer batteries.