Separators For Lithium-ion Batteries Research Articles

Polyvinylidene fluoride gel‐polyethylene composite separator optimizing the interface compatibility between the separator and the electrode

AbstractThe interface issue concerning lithium dendrite formation between the separator and electrode remains a significant impediment to the further advancement of lithium‐ion batteries (LIB). Due to the inadequate interface compatibility between the conventional polyolefin separator and the electrode, there is a propensity for lithium dendrite growth. In this work, the surface of the polyethylene (PE) separator is coated with polyvinylidene fluoride (PVDF) gel using a simple phase transformation method, resulting in the preparation of a composite separator consisting of PE and PVDF. The results demonstrate an enhanced interface compatibility following the introduction of the gel layer, with a polarization voltage as low as 0.14 V observed after 250 h of cycling. Additionally, the ionic conductivity of the PE/PVDF composite separator (1.77 mS cm−1) is enhanced, attributed to the incorporation of F functional group in PVDF gel, which could facilitate the formation of a rapid ion transport pathway through the interaction between F functional group and Li+. After the introduction of the gel layer, the discharge capacity of the battery after 250 cycles measures ~1.28 mAh, with a mere 27% decay in capacity. This study presents a novel concept for the design of composite separator in LIB.

Rheological and light scattering analyses for characterizing phase separation of polymer solutions in lithium-ion battery separator coating system

Rheological and light scattering analyses for characterizing phase separation of polymer solutions in lithium-ion battery separator coating system

Electrospun Silicon Dioxide/poly(vinylidene fluoride) Nanofibrous Membrane Comprising a Skin Multicore-Shell Nanostructure as a New High-Heat-Resistant Separator for Lithium-Ion Polymer Batteries.

Porous silicon dioxide (SiO2)/poly(vinylidene fluoride) (PVdF), SiO2/PVdF, and fibrous composite membranes were prepared by electrospinning a blend solution of a SiO2 sol-gel/PVdF. The nanofibers of the SiO2/PVdF (3/7 wt. ratio) blend comprised skin and nanofibrillar structures which were obtained from the SiO2 component. The thickness of the SiO2 skin layer comprising a thin skin layer could be readily tuned depending on the weight proportions of SiO2 and PVdF. The composite membrane exhibited a low thermal shrinkage of ~3% for 2 h at 200 °C. In the prototype cell comprising the composite membrane, the alternating current impedance increased rapidly at ~225 °C, and the open-circuit voltage steeply decreased at ~170 °C, almost becoming 0 V at ~180 °C. After being exposed at temperatures of >270 °C, its three-dimensional network structure was maintained without the closure of the pore structure by a melt-down of the membrane.

Eco-Friendly Lithium Separators: A Frontier Exploration of Cellulose-Based Materials.

Lithium-ion batteries, as an excellent energy storage solution, require continuous innovation in component design to enhance safety and performance. In this review, we delve into the field of eco-friendly lithium-ion battery separators, focusing on the potential of cellulose-based materials as sustainable alternatives to traditional polyolefin separators. Our analysis shows that cellulose materials, with their inherent degradability and renewability, can provide exceptional thermal stability, electrolyte absorption capability, and economic feasibility. We systematically classify and analyze the latest advancements in cellulose-based battery separators, highlighting the critical role of their superior hydrophilicity and mechanical strength in improving ion transport efficiency and reducing internal short circuits. The novelty of this review lies in the comprehensive evaluation of synthesis methods and cost-effectiveness of cellulose-based separators, addressing significant knowledge gaps in the existing literature. We explore production processes and their scalability in detail, and propose innovative modification strategies such as chemical functionalization and nanocomposite integration to significantly enhance separator performance metrics. Our forward-looking discussion predicts the development trajectory of cellulose-based separators, identifying key areas for future research to overcome current challenges and accelerate the commercialization of these green technologies. Looking ahead, cellulose-based separators not only have the potential to meet but also to exceed the benchmarks set by traditional materials, providing compelling solutions for the next generation of lithium-ion batteries.

High-Safety Lithium-Ion Battery Separator with Adjustable Temperature Function Inspired by the Sugar Gourd Structure.

As the power core of an electric vehicle, the performance of lithium-ion batteries (LIBs) is directly related to the vehicle quality and driving range. However, the charge-discharge performance and cycling performance are affected by the temperature. Excessive temperature can cause internal short circuits and even lead to safety issues, such as thermal runaway. The separator plays a crucial role in protecting the battery from regular operation, preventing direct touch between the cathode and the anode while allowing the transport of lithium ions. In this study, we have designed a thermoregulating separator in the shape of calabash, which uses melamine-encapsulated paraffin phase change material (PCM) with a wide enthalpy (0-168.52 J g-1) to dissipate the heat generated inside the battery promptly. Under extra-long-use conditions, the heat emitted by the battery is absorbed by the PCM without causing a significant temperature rise that triggers thermal runaway. The PCM separator can effectively suppress the temperature increase caused by battery penetration. Due to the unique structure of the PCM, the battery is short-circuited; it can significantly delay the internal temperature rise of the battery and quickly dissipate the heat, which is consistent with the characteristics of natural calabash in nutrient absorption and water diffusion, improving the melting and heat storage efficiency of the PCM. The design of the phase change separator provides an effective reference for overheat protection and improved safety in lithium-ion batteries.

Evaluation of asymmetric poly(vinylidene fluoride)-coated polyimide separator with three-dimensionally homogeneous microporous structure for high-safety lithium-ion battery

Safety hazards associated with separators in lithium-ion batteries are more pronounced in light of the significant improvement of energy density of batteries, hindering their wide application. In this research, asymmetric poly (vinylidene fluoride) (PVDF)-coated polyimide separators with three-dimensionally homogeneous microporous (3DHM API/PVDF) structure are prepared, in which a PVDF layer with a thickness of 6 μm on one side of polyimide. Polyimide, as the base film, has a high heat-resistant temperature which ensures that as-prepared separators will not be shrunk and burned. The coated PVDF layer imparts 3DHM API/PVDF with thermal shutdown function at 175 °C due to the melting of PVDF. The temperature difference between the shutdown and meltdown temperature is over 100 °C, ensuring that the LIB assembled with 3DHM API/PVDF is safe for use. Moreover, the interconnected microporous structure of the separator facilitates the formation of 3D Li+ transport pathways and uniformity of lithium deposition, suppressing lithium dendrite growth. The coin cells assembled by 3DHM API/PVDF exhibit similar electrochemical performance to that of a commercial polypropylene separator at room temperature. Therefore, the novel 3DHM API/PVDF separator may be a promising candidate for a significantly safer LIB.

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.