Separators For Lithium-ion Batteries Research Articles

Tartaric Acid Cross-Linking Polyvinyl Alcohol as Degradable Separators for Rechargeable Lithium Ion Batteries.

The escalating focus on environmental concerns and the swift advancement of eco-friendly biodegradable batteries raises a pressing demand for enhanced material design in the battery field. The traditional polypropylene (PP) that is monopolistically utilized in the commercial LIBs is hard to recycle. In this work, we prepare a novel water degradable separators via the cross-linking of polyvinyl alcohol (PVA) and dibasic acid (tartaric acid, TA). Through the integration of non-solvent liquid-phase separation, we successfully produced a thermally stable PVA-TA membrane with tunable thickness and a high level of porosity. These specially engineered PVA-TA separators were implemented in LiFePO4 (LFP)|separator|Li cells, resulting in superior multiplicative performance and achieving a capacity of 88 mAh g-1 under 5 C. Additionally, the straightforward small molecule cross-linking technique significantly reduced the crystalline region of the polymer, thereby enhancing ionic conductivity. Notably, after cycling, the PVA-TA separators can be easily dissolved in 95 °C hot water, enabling its reutilization for the production of new PVA-TA separators. Therefore, this work introduces a novel concept to design green and sustainable separators for recyclable lithium batteries.

Utilizing methacrylated lignin as a sustainable macro-crosslinker for synthesizing innovative PVA/AMPS composites crosslinked hydrogel nanofibers: A potential application for lithium-ion battery separators

There are significant issues with commercial separators that must be resolved before they can be used in high-energy-density batteries. These problems include low porosity, poor electrolyte wetting, and low mechanical properties. This study presents a facile method for preparing composite crosslinked hydrogel nanofibers of polyvinyl alcohol (PVA) with 2-acrylamide-2-methylpropanesulfonic acid (AMPS) for lithium-ion battery separators by utilizing methacrylated lignin (LMA) as a bio-based crosslinker. Initially, LMA was synthesized by grafting glycidyl methacrylate (GMA) onto lignin via esterification. Subsequently, a crosslinked hydrogel nanofiber membrane (PVA/AMPS-LMA) was electrospun with varying LMA fractions, which were polymerized by combining free radical copolymerization and esterification reactions. The effectiveness of LMA as a crosslinker was assessed against the N, N′-methylene bisacrylamide (MBA). The study showed that using LMA as a crosslinker significantly improved the membrane's properties. The PVA/AMPS-LMA separator displayed superior features such as mechanical strength, thermal stability, porosity, electrolyte uptake, ionic conductivity, and lithium-ion transference number, when compared with PVA/AMPS, PVA, and Celgard separators. Specifically, the PVA/AMPS-LMA separator demonstrated a high mechanical strength of 24.9 MPa, strong thermal stability at 170 °C with no shrinkage, high porosity (84.3 %), and electrolyte uptake (661.4 %). It also exhibited exceptional ionic conductivity (2.75 mS/cm) and a notable lithium-ion transference number (tLi+ = 0.717). In coin batteries, the PVA/AMPS-LMA separator retained over 96 % capacity (142.4 mAh/g) after 200 cycles at 1C. This performance exceeded that of PVA/AMPS, PVA, and Celgard separators, suggesting that PVA/AMPS-LMA separators have the potential to replace their commercial counterparts.

Functionalized γ-Boehmite Covalent Grafting Modified Polyethylene for Lithium-Ion Battery Separator.

In the field of lithium-ion batteries, the challenges posed by the low melting point and inadequate wettability of conventional polyolefin separators have increased the focus on ceramic-coated separators. This study introduces a highly efficient and stable boehmite/polydopamine/polyethylene (AlOOH-PDA-PE) separator. It is crafted by covalently attaching functionalized nanosized boehmite (γ-AlOOH) whiskers onto polyethylene (PE) surfaces. The presence of a covalent bond increases the stability at the interface, while amino groups on the surface of the separator enhance the infiltration of the electrolyte and facilitate the diffusion of lithium ions. The PE-PDA-AlOOH separator, when used in lithium-ion batteries, achieves a discharge capacity of 126 mAh g-1 at 5 C and retains 97.1% capacity after 400 cycles, indicating superior cycling stability due to its covalently bonded ceramic surface. Thus, covalent interface modification is a promising strategy to prevent delamination of ceramic coatings in separators.

Fabrication of rice-straw lignin/polyacrylonitrile composite membrane for lithium-ion battery separator

This study outlines the successful fabrication of composite membrane using rice-straw lignin/polyacrylonitrile (L-PAN) via electrospinning method, and evaluated as a lithium-ion battery separator. L-PANs exhibited higher porosity and superior electrolyte wettability compared to the commercial Celgard 2300. Remarkably, even after exposure to 150 °C for an hour, L-PANs showed minimal changes, whereas Celgard 2300 experienced notable shrinkage. As a separator for Li/LiFePO4 batteries, L-PANs demonstrated outstanding capacity retention of 97.7 % over 200 cycles and superior cycling performance compared to Celgard 2300. Collectively, this research offers a promising approach to valorizing waste rice straw resources and expanding the application of lignin in the field of lithium-ion battery.

Control of Pore Sizes in Epoxy Monoliths and Applications as Sheet-Type Adhesives in Combination with Conventional Epoxy and Acrylic Adhesives.

Materials with monolithic structures, such as epoxy monoliths, are used for a variety of applications, such as for column fillers in gas chromatography and HPLC, for separators in lithium-ion batteries, and for precursor polymers for monolith adhesion. In this study, we investigated the fabrication of epoxy monoliths using 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C) as the tetrafunctional epoxy and 4,4'-methylenebis(cyclohexylamine) (BACM) as the amine curing agent to control pore diameters using polyethylene glycols (PEGs) of differing molecular weights as the porogenic agents. We fabricated an epoxy monolith with micron-order pores and high strength levels, and which is suitable for the precursors of composite materials in cases where smaller PEGs are used. We discussed the effects of the porous structures of monoliths on their physical properties, such as tensile strength, elongation, elastic modulus, and glass transition temperatures. For example, epoxy monoliths prepared in the presence of PEGs exhibited an elastic modulus less than 1 GPa at room temperature and Tg values of 175-187 °C, while the epoxy bulk thermoset produced without any porogenic solvent showed a high elastic modulus as 1.8 GPa, which was maintained at high temperatures, and a high Tg of 223 °C. In addition, the unique adhesion characteristics of epoxy monolith sheets are revealed as a result of the combinations made with commercial epoxy and acrylic adhesives. Epoxy monoliths that are combined with conventional adhesives can function as sheet-type adhesives purposed with avoiding problems when only liquid-type adhesives are used.

Facile fabrication of regenerated cellulose-based separators for high-performance lithium-ion batteries by regulating degrees of polymerization

Cellulose-based separators have great application prospects in the field of lithium-ion batteries (LIBs) due to their excellent wettability and thermal stability. However, most current cellulose-based separators come from high-cost nanocellulose and bacterial cellulose. Herein, regenerated cellulose (RC) separators were prepared from dissolving pulp with different degrees of polymerization (DPs) by using the NaOH/urea/thiourea dissolution system as well as a nonsolvent-induced phase separation method. The results showed that the DP of cellulose had a significant influence on the mechanical properties, pore structure, and electrochemical properties of the resultant RC separator. An appropriate increase in the DP could improve the mechanical strength, porosity, and ionic conductivity of the separator. The RC separator with a DP of 599 exhibited the best performance with a porosity of 56.1 %, an average pore size of 305 nm, an electrolyte uptake of 339 %, a tensile strength of 38.3 MPa, and an ionic conductivity of 1.88 mS·cm−1. The lithium-ion battery prepared with the optimal RC separator had a specific capacity of 156.55 mAh/g for 100 cycles at a current density of 0.5 C and a coulombic efficiency of more than 96 %, which was a clear advantage over the commercially available Celgard2400 and cellulose separators. This work makes contributions to the development of high-performance LIBs separators from cellulose.

A polyimide separator inlaid by methylsilyl-modified silica aerogels for high thermal safety and low polarization lithium-ion battery

The separator is a crucial component of lithium-ion batteries, playing a vital role in ion transfer and preventing polarization of the battery. To solve the problem of poor thermal safety of separators in lithium-ion batteries, in this work, three types of hydrophobic silica aerogels are compared. A suitable separator is fabricated by adding hydrophobic silica aerogels with monomethylsilyl as a modifier to pure polyimide. The aerogel composite separator displays a highly cross-linked three-dimensional nanoporous network, a low thermal shrinkage rate (<4 % at 200 °C), and high thermal stability (peak temperature of 670 °C) and oxygen index (>45 %). In addition, owing to the introduced hydrophobic functional groups of Si–CH3, the prepared separator decreases the polarization of the lithium-ion batteries and leads to improved power performance and cycle stability (its discharge voltage difference is 0.42 V higher than that of Celgard 2325 at 5 C). This work provides a new method of improving the safety and simultaneously reducing the polarization of lithium-ion batteries, which has promising application potential in power batteries.

Ternary composites of poly(vinylidene fluoride-co-hexafluoropropylene) with silver nanowires and titanium dioxide nanoparticles as separator membranes for lithium-ion batteries

In the realm of polymer composites, there is growing interest in the use of more than one filler for achieving multifunctional properties. In this work, a composite separator membrane has been developed for lithium-ion battery application, by incorporating conductive silver nanowires (AgNWs) and titanium dioxide (TiO2) nanoparticles into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer matrix. The composite membranes were manufactured by solvent casting and thermally induced phase separation, with total filler content varying up to 10 wt%. The ternary composites composites present improved mechanical characteristics, ionic conductivity and lithium transfer number compared to the neat polymer matrix. On the other hand, the filler type and content within the composite has little bearing on the morphology, polymer phase, or thermal stability. Once applied as a separator in lithium-ion batteries, the highest discharge capacity value was obtained for the 5 wt% AgNWs/5 wt% TiO2/PVDF-HFP membrane at different C-rates, benefiting from the synergetic effect from both fillers. This work demonstrates that higher battery performance can be achieved for next-generation lithium-ion batteries by using separator membranes based on ternary composites.

Mechanical Behavior of Lithium-Ion Battery Separators under Uniaxial and Biaxial Loading Conditions.

The mechanical integrity of two commercially available lithium-ion battery separators was investigated under uniaxial and biaxial loading conditions. Two dry-processed microporous films with polypropylene (PP)/polyethylene (PE)/polypropylene (PP) compositions were studied: Celgard H2010 Trilayer and Celgard Q20S1HX Ceramic-Coated Trilayer. The uniaxial tests were carried out along the machine direction (MD), transverse direction (TD), and diagonal direction (DD). In order to generate a state of in-plane biaxial tension, a pneumatic bulge test setup was prioritized over the commonly performed punch test in an attempt to eliminate the effects of contact friction. The biaxial flow stress-strain behavior of the membranes was deduced via the Panknin-Kruglov method coupled with a 3D Digital Image Correlation (DIC) technique. The findings demonstrate a high degree of in-plane anisotropy in both membranes. The ceramic coating was found to negatively affect the mechanical performance of the trilayer microporous separator, compromising its strength and stretchability, while preserving its failure mode. Derived from experimentally calibrated constitutive models, a finite element model was developed using the explicit solver OpenRadioss. The numerical model was capable of predicting the biaxial deformation of the semicrystalline membranes up until failure, showing a fairly good correlation with the experimental observations.

Alkali etching enhanced polyimide-based three-layer composite separator for lithium-ion batteries

Alkali etching enhanced polyimide-based three-layer composite separator for lithium-ion batteries

Poly(vinylidene fluoride)-based composite membranes with continuous metal–organic framework layer for high-performance separators of lithium-ion batteries

Lithium-ion batteries (LIBs) play a critical role in modern portable electronic devices, electric vehicles, and wearable electronics. However, the formation of lithium dendrites during cycling results in serious capacity loss and safety risks owing to the heterogeneous transport and deposition of Li+. In this work, we present a poly(vinylidene fluoride) (PVDF)-based composite membrane with a continuous metal–organic framework (MOF) layer as high-performance separators in LIBs. The PVDF membranes with uniform pore structures are prepared by using superspreading strategy, facilitating the growth of continuous and controllable MOF layer inside the membranes via a simple interfacial synthesis. The as prepared PVDF-MOF composite membranes display uniform and continuous subnanochannels with connected opened metal sites (OMS), which can generate a homogeneous transport of Li+. Taking advantages of the low impedance (∼2 Ω), high ionic conductivity (0.61 mS cm−1), and high stripping peak current (0.89 mA cm−2), the PVDF-MOF composite separators efficiently prevent the uneven deposition and the generation of lithium dendrites. Moreover, the PVDF-MOF-based LIBs showed a high capacity retention rate of 81.0 % after 250 cycles. This strategy paves a new avenue for MOF-based composite separator in LIBs.

Status and Prospect of Two-Dimensional Materials in Electrolytes for All-Solid-State Lithium Batteries.

Replacing liquid electrolytes and separators in conventional lithium-ion batteries with solid-state electrolytes (SSEs) is an important strategy to ensure both high energy density and high safety. Searching for fast ionic conductors with high electrochemical and chemical stability has been the core of SSE research and applications over the past decades. Based on the atomic-level thickness and infinitely expandable planar structure, numerous two-dimensional materials (2DMs) have been exploited and applied to address the most critical issues of low ionic conductivity of SSEs and lithium dendrite growth in all-solid-state lithium batteries. This review introduces the research process of 2DMs in SSEs, then summarizes the mechanisms and strategies of inert and active 2DMs toward Li+ transport to improve the ionic conductivity and enhance the electrode/SSE interfacial compatibility. More importantly, the main challenges and future directions for the application of 2DMs in SSEs are considered, including the importance of exploring the relationship between the anisotropic structure of 2DMs and Li+ diffusion behavior, the exploitation of more 2DMs, and the significance of in situ characterizations in elucidating the mechanisms of Li+ transport and interfacial reactions. This review aims to provide a comprehensive understanding to facilitate the application of 2DMs in SSEs.

Thermally stable poly-aromatic solid electrolyte coated polyethylene membrane as high-performance lithium-ion battery separator

Improving the dimensional stability and electrolyte wettability of polyolefin separators is crucial to enhancing the safety and performance of power lithium-ion batteries (LIBs). In this work, composited separators that significantly improve both thermal stability and solvent wettability are prepared by coating polyaromatic solid electrolyte (sulfonated poly(aryl ether ketone), SPAEK) onto the surface of commercial polyethylene (PE) separators. Interestingly, the coating layer formed by SPAEK with a 60% sulfonation degree exhibits abundant porous structure owing to the polar sulfonic group inducing a retarded phase separation process. The polyelectrolyte coating layer enables both super-electrolyte affinity and higher electrolyte uptake of the composite separator. Moreover, the composited separator presents much better comprehensive properties, including thermal stability and ionic conductivity. As a result, the SPAEK-coated composite separator assembles LiNi0.83Co0.11Mn0.06O2 (NCM811)/Li battery exhibits a higher capacity retention rate of 84.01% at 2 C with a specific capacity of 151.25 mAh g−1 after 200 cycles. Hence, this modified separator is a potential material that facilitates high performance and safety for Li-ion batteries.

Solution Blow Spinning of the Benzimidazole-Containing Aramid Nanofibers for Separators of Lithium-Ion Batteries.

Nanofibers based on high-performance polymers are much highlighted in recent studies toward advanced lithium-ion batteries. Herein, we demonstrate one scalable poly(ethylene oxide) (PEO)-assisted solution blow spinning strategy for the preparation of heterocyclic aramid (HA) nanofibers of poly(p-phenylene-benzimidazole-terephthalamide). The incorporation of PEO is essential to improve the spinnability of the HA solution achieved directly through the low-temperature-solution copolymerization process. Additionally, the flexible PEO with a strong H-bonding affinity is also utilized as the molecular zipper to adjust the pore size of the nanofiber membrane during the post-treatment process. The obtained membrane combines the good wettability of PEO to the liquid electrolytes, with outstanding mechanical strength, modulus, toughness, and environmental resistance of HA. The nonwoven separator membranes with a porosity of 83.6% exhibited excellent comprehensive performance, which could be seen not only on the high tensile strength (68.2 MPa), modulus (3.0 GPa), and toughness but also on the high thermal stability (Td > 405 °C) and flame retardancy, as well as the high electrolyte uptake (302.4%). The ion conductivity of the porous separators reached 0.83 mS/cm, with the bulk resistance dropping to 1/4 of the reference polypropylene separator. In the assembly of the Li/LiFePO4 half battery, the HA separators displayed improved discharge specific capacity and high retention in both rate capability and cycling tests, providing the potential industrial preparation for advanced lithium-ion batteries.

Principles and Requirements of Battery Membranes: Ensuring Efficiency and Safety in Energy Storage

This critical review highlights the latest improvements and special features regarding the membrane separators available for lead-acid, alkaline, metal-metal, metal-gas, and metal-ion batteries such as lithium-ion. In the recent years, there has been a surge in the intensive work aimed at developing innovative separators for rechargeable lithium-ion batteries, for example, electric vehicles (EVs), portable electronics and for energy storage in power grid. The separator finds itself in a very important place as it provides physical separation between two electrodes. It also acts as an electrical insulator. This separator is known as an electrolyte gateway which helps the movement of ions during charge/discharge cycles. This review addresses the requirements for battery separators and explains the structure and properties of various types of membrane separators; there are several types of membranes such as microporous membranes, modified microporous membranes, nonwoven mats, composite membranes and electrolyte membranes. Similarly, each type of separator has inherent advantages and disadvantages which in turn directly affects the performance of batteries. This review article systematically deals with the structures and working principle of separators, properties and main requirements and their characterization method of separators, generation, improvements, and function assessments of these separators. Furthermore, this study also enlightens the emerging research path and future prospects.

Effect of thermal processing conditions on the structure and properties of porous PENK/PVDF composite films and its application as lithium-ions separators

By developing high-performance lithium-ion battery technology, the demands on the design of separator modification have increased. However, battery performance and safety are limited by conventional polyolefin separators' poor thermal resistance and electrolyte wettability. Biphenyl-type poly (arylene ether nitrile ketone) (BP-PENK) is synthesized. PENK polymers are a class of poly (aryl ether) with excellent properties of both Poly (aryl ether nitrile) (PEN) and Poly (ether ketone) (PEEK). The BP-PENK/PVDF composite film is further processed by non-solvent induced phase separation (NIPS), and the impact of annealing temperatures on the thermal resistance and crystalline phase structure of composite separators has been studied. The composite separator owns enhanced ionic conductivity, excellent electrolyte wettability, and superior thermal durability. The cell equipped with the composite separator has a discharge-specific capacity of 146.5 mAh·g−1 and a capacity retention rate of 86.64 %. In this way, A novel approach to producing lithium-ion battery separators that possess outstanding electrochemical properties and high thermal durability is provided.

Al2O3 Thin Layer Formed inside Porous Membrane Using Spray Synthesis Method and Its Application

Aluminum oxide (Al2O3) films have been investigated for use in various applications, and numerous deposition techniques have been reported. The spray synthesis method has the advantage of forming a thin layer of crystal at low temperatures using the appropriate precursors. A precursor prepared by diluting Methylaluminoxane with N-methyl pyrrolidone was sprayed onto a porous membrane while varying conditions such as the substrate temperature, feeding speed, and spray amount. The solution penetrated the film during spray application, and the ultra-thin layers deposited on the side wall of the internal pores were observed using a cross-sectional transmission electron microscope (XTEM). The lattice image obtained using the TEM and the composition analysis conducted using a scanning TEM and an energy-dispersive X-ray spectroscope suggest that this thin layer is a layer of Al2O3. The formation of Al2O3 occurred at lower temperatures than in previous reports. This is a major advantage for applications with low-melting-point materials. The most suitable spraying conditions were determined based on the state of deposition on the surface and inside the membrane. These conditions were applied to a three-layer separator for lithium-ion batteries and their effect on thermal stability was investigated. Through heating experiments and XRD analysis, it was confirmed that the shrinkage and melting of the separator are suppressed by spraying. This process can be expected to have wide applications in low-melting-point materials such as polyolefin.

Prediction and Computer Simulation of Pore Intersection in Lithium-Ion Battery Separator Membranes

The separator membrane is one of the four key materials of a lithium-ion battery, and the size of the separator membrane pores plays an important role on the internal resistance and safety of the battery. In this study, firstly, the relationship between the average pore size and the pore center to center distance with different porosity ratios in the separator membrane was analyzed with statistical theory. Then, a mathematical model was established to predict the probability of intersections and merging of the pores. In the end, the probability of intersections of pores with different porosity ratios were calculated and simulated; the differences between the results obtained from the two ways were 1.16%, 1.47% and 4.16%, when the porosity ratios were 21.36%, 40.16% and 53.34%, respectively, which indicated that the prediction model had good accuracy.

3D porous structure imaging of membranes for medical devices using scanning probe microscopy and electron microscopy: from membrane science points of view.

The evolution of hemodialysis membranes (dialyzer, artificial kidney) was remarkable, since Dow Chemical began manufacturing hollow fiber hemodialyzers in 1968, especially because it involved industrial chemistry, including polymer synthesis and membrane manufacturing process. The development of hemodialysis membranes has brought about the field of medical devices as a major industry. In addition to conventional electron microscopy, scanning probe microscopy (SPM), represented by atomic force microscopy (AFM), has been used in membrane science research on porous membranes for hemodialysis, and membrane science contributes greatly to the hemodialyzer industry. Practical studies of membrane porous structure-function relationship have evolved, and methods for analyzing membrane cross-sectional morphology were developed, such as the ion milling method, which was capable of cutting membrane cross sections on the order of molecular size to obtain smooth surface structures. Recently, following the global pandemic of SARS-CoV-2 infection, many studies on new membranes for extracorporeal membrane oxygenator have been promptly reported, which also utilize membrane science researches. Membrane science is playing a prominent role in membrane-based technologies such as separation and fabrication, for hemodialysis, membrane oxygenator, lithium ion battery separators, lithium recycling, and seawater desalination. These practical studies contribute to the global medical devices industry.

Fabrication of coaxially electrospun PEI@PVDF-HFP fibrous membrane as flame-retardant and anti-shrink separator for lithium-ion battery

A novel core–shell nanocomposite fiber membrane was fabricated in this work by coaxial electrospinning using poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) as shell material and polyetherimide (PEI) as core material. The PEI core has good heat resistance and mechanical strength, serving as a stable skeleton support. At the same time, the gel shell is conducive to enhancing the electrolyte affinity, thereby promoting the rapid transmission of Li+. As a result, the Li/LiCoO2 batteries with the fabricated separator present an excellent first discharge capacity of 178.8 mAh g−1 at 0.2C and capacity retention rate of 89.7 % after 200 cycles. Even running at high temperature (65 °C), the PEI@PVDF-HFP separator still enables a steady charging/discharging performance. Therefore, the PEI@PVDF-HFP nanocomposite separator can be an extraordinary candidate for high-safety lithium-ion batteries.