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.

Etched ion-track membranes as tailored separators in Li-S batteries.

Lithium-sulfur (Li-S) batteries are considered a promising next generation alternative to lithium-ion batteries for energy storage systems due to its high energy density. However, several challenges, such as the polysulfide redox shuttle causing self-discharge of the battery, remain unresolved. In this paper, we explore the use of polymer etched ion-track membranes as separators in Li-S batteries to mitigate the redox shuttle effect. Compared to commercial separators, their unique advantages lie in their very narrow pore size distribution, and the possibility to tailor and optimize the density, geometry, and diameter of the nanopores in an independent manner. Various polyethylene terephthalate membranes with diameters between 22 and 198 nm and different porosities were successfully integrated into Li-S coin cells. The reported coulombic efficiency of up to 97% with minor reduction in capacity opens a pathway to potentially address the polysulfide redox shuttle in Li-S batteries using tailored membranes.

Biopolymer separators from polydopamine-functionalized bacterial cellulose for lithium-sulfur batteries.

The advancement of the lithium-sulfur (Li-S) batteries is immensely impeded by two main challenges: polysulfide shuttling between the electrodes and Li dendrite formation associated with the Li-metal anode. To tackle these challenges, we synthesized a polydopamine coated bacterial cellulose (PDA@BC) separator in a way to create physical and chemical traps for the shuttling polysulfides and to control the Li+ flux. While nanocellulose offers its dense network as a physical trap, the presence of polydopamine in the separator offers polar functional groups which not only has a high binding energy towards the polysulfides but also helps in redistribution of the Li+ ions across it. The electrochemical and physiochemical results suggest that the synthesized separator can have practical applicability owing to its superior performance compared to a commercial separator. The Li-S batteries assembled with this separator showed a specific discharge capacity of 1449 mAh/g at 0.1C and 877 mAh/g at 1C, and a capacity fade of 0.03 % per cycle over 650 cycles at 1C. Using a PDA@BC separator, a practical Li-S battery cell with S loading of 7.5 mg cm-2 (and E/S ratio of 10 µLmg-1, 82 % S ratio) was also tested at 1C, which delivered a capacity of âˆ¼ 6 mAh cm-2 for 500 cycles.

Ultra-thin nanosheets decorated in-situ S-doped 3D interconnected carbon network as interlayer modified Li-S batteries separator for accelerating adsorption-catalytic synergistic process of LiPSs.

The shuttle effect of soluble lithium polysulfides (LiPSs) is primarily responsible for the unstable performance of lithium-sulfur (Li-S) batteries, which has severely impeded their continued development. In order to solve this problem, a special strategy is proposed. Specifically, ultra-thin NiCo based layered double hydroxides (named LDH or NiCo-LDH) nanosheets are implanted into a pre-designed 3D interconnected carbon networks (SPC) to obtain porous composite materials (named SPC-LDH).During the operation of the battery, the 3D interconnected porous carbon mesh was the first to rapidly adsorb LiPSs, and then the LDH on the surface of the carbon mesh was used to realize the catalytic conversion of LiPSs. This facilitates the electrochemical conversion reaction between S substances while addressing the "shuttle effect". As a result, the battery maintains a discharge capacity of 1401.9, 1114.3, 975.5, 880.7, 760.4 and 679.6 mAh g-1 at the current densities of 0.1, 0.2, 0.5, 1, 2 and 3C, respectively. After 200 cycles at 2C, the battery's capacity stays at 732.9 mAh g-1, meaning that the average rate of capacity decay is only 0.007 % per cycle. Moreover, in-situ XRD demonstrates the critical function of PP/SPC-LDH separators in inhibiting LiPSs and encouraging Li2S transformation. The strong affinity of SPC-LDH for Li2S6 is also confirmed by density functional theory (DFT) calculation, offering more theoretical support for the synergistic adsorption process. This work offers a compelling method to develop modified separator materials that can counteract the "shuttle effect" in Li-S batteries.

Composite Membrane Containing Titania Nanofibers for Battery Separators Used in Lithium-Ion Batteries.

In order to improve the electrochemical performance of lithium-ion batteries, a new kind of composite membrane made using inorganic nanofibers has been developed via electrospinning and the solvent-nonsolvent exchange process. The resultant membranes present free-standing and flexible properties and have a continuous network structure of inorganic nanofibers within polymer coatings. Results show that polymer-coated inorganic nanofiber membranes have better wettability and thermal stability than those of a commercial membrane separator. The presence of inorganic nanofibers in the polymer matrix enhances the electrochemical properties of battery separators. This results in lower interfacial resistance and higher ionic conductivity, leading to the good discharge capacity and cycling performance of battery cells assembled using polymer-coated inorganic nanofiber membranes. This provides a promising solution via which to improve conventional battery separators for the high performance of lithium-ion batteries.

Class of Boehmite/Polyacrylonitrile Membranes with Different Thermal Shutdown Temperatures for High-Performance Lithium-Ion Batteries.

Nowadays, lithium-ion batteries are required to have a higher energy density and safety because of their wide applications. Current commercial separators have poor wettability and thermal stability, which significantly impact the performance and safety of batteries. In this study, a class of boehmite particles with different grain sizes was synthesized by adjusting hydrothermal temperatures and used to fabricate boehmite/polyacrylonitrile (BM/PAN) membranes. All of these BM/PAN membranes can not only maintain excellent thermal dimensional stability above 200 °C but also have good electrolyte wettability and high porosity. More interestingly, the BM/PAN membranes' thermal shutdown temperature can be adjusted by changing the grain size of boehmite particles. The lithium-ion batteries assembled with BM/PAN separators exhibit different thermal stability phenomena at 150 °C and have excellent rate performance and cycle stability at room temperature. After 120 cycles at 1C, the LiFePO4 half-cell assembled by the best BM/PAN separator has almost unchanged discharge capacity, whereas the capacity retention of Celgard 2325 is only about 85%. Meanwhile, the NCM523 half-cell assembled with the best BM/PAN separator shows superb cycle stability after 500 cycles at 8C, with a capacity retention of 79% compared with 56% for Celgard 2325.

Engineering Polymer-Based Porous Membrane for Sustainable Lithium-Ion Battery Separators.

Due to the growing demand for eco-friendly products, lithium-ion batteries (LIBs) have gained widespread attention as an energy storage solution. With the global demand for clean and sustainable energy, the social, economic, and environmental significance of LIBs is becoming more widely recognized. LIBs are composed of cathode and anode electrodes, electrolytes, and separators. Notably, the separator, a pivotal and indispensable component in LIBs that primarily consists of a porous membrane material, warrants significant research attention. Researchers have thus endeavored to develop innovative systems that enhance separator performance, fortify security measures, and address prevailing limitations. Herein, this review aims to furnish researchers with comprehensive content on battery separator membranes, encompassing performance requirements, functional parameters, manufacturing protocols, scientific progress, and overall performance evaluations. Specifically, it investigates the latest breakthroughs in porous membrane design, fabrication, modification, and optimization that employ various commonly used or emerging polymeric materials. Furthermore, the article offers insights into the future trajectory of polymer-based composite membranes for LIB applications and prospective challenges awaiting scientific exploration. The robust and durable membranes developed have shown superior efficacy across diverse applications. Consequently, these proposed concepts pave the way for a circular economy that curtails waste materials, lowers process costs, and mitigates the environmental footprint.

Coupled Effect of Low Temperature and Electrolyte Immersion on the Tensile Properties of Separators in Lithium-Ion Batteries.

The performance degradation at low temperatures and frequent safety accidents have aggravated security risks and inhibited the long-term service of lithium-ion batteries (LIBs). As a key component of LIBs, the separator has a great impact on the performance and safety of the battery. In this study, tensile tests of two commercial polyolefin separators (Celgard 2325 and Celgard PE) are performed under low-temperature and immersion conditions. Four representative temperature points and dimethyl carbonate [(DMC), the common solvent in electrolytes] are selected to investigate the coupling effect on the mechanical properties of the separators. The results show that both the separators have anisotropy, but the performance of Celgard 2325 varies more significantly than that of Celgard PE along different directions. Additionally, it is found that with a decrease in the temperature, the tensile strength of the two separators increases, while the elongation decreases. Electrolyte immersion induces a softening tendency in Celgard 2325. Due to the special effect of the residual electrolyte on polyethylene fibers, Celgard PE shows the opposite result. Furthermore, the effect of low temperature is revealed by the analysis of the crystallinity and molecular structure, which can be obtained by X-ray diffraction and Raman spectroscopy, respectively. In addition, the contact angle is measured to describe the wettability variation related to low temperature. The present work provides a theoretical basis and experimental data for the application and development of separators.

Roll-to-Roll Gravure Coating of PVDF on a Battery Separator for the Enhancement of Thermal Stability.

The polyethylene lithium-ion battery separator is coated with a polymer by means of a roll-to-roll (R2R) gravure coating scheme to enhance the thermal stability. The polyvinylidene fluoride (PVDF) or polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) is gravure-coated, and the pores are fabricated based on online nonsolvent-induced phase separation (NIPS). N-methylpyrrolidone is used as a solvent, and deionized water or a methanol mixture thereof is exploited as a nonsolvent in NIPS. Scanning electron microscopy confirms that the polymer film is formed and that the pores are well developed. The thermal shrinkage decreased by 20.0% and 23.2% compared to that of the bare separator due to the coating of PVDF and PVDF-HFP, respectively. The R2R gravure coating scheme is proven to be fully functional to tailor the properties of lithium-ion battery separators.

Silk fibroin and sericin polymer blends for sustainable battery separators.

Natural polymers are a promising alternative for reducing the environmental impact of batteries. For this reason, it is still necessary to study their behavior and implement its use in these devices, especially in separator membranes. This work reports on new separator membranes based on silk fibroin (SF) and silk sericin (SS) prepared by salt leaching method. The effect of the different SS relative content on the physiochemical properties of the membranes and on the electrochemical performance of the corresponding batteries with lithium iron phosphate (LFP) as cathodes has been reported. It is observed that the increasing of SS content leads to a decrease of the overall crystallinity of the membranes. All SF/SS membranes presented a well-defined porosity above 75% with a uniform distribution of interconnected micropores. The electrolyte uptake and the ionic conductivity are dependent on the relative SS content. The addition of 10 wt% of SS into SF membranes, induce a high ionic conductivity of 4.09 mS.cm-1 and high lithium transference number (0.52), due to the improvement of the Li+ ions conduction paths within the blended structure. Charge/discharge tests performed in Lithium/C-LFP half-cells reveal a discharge capacity of 85 mAh.g-1 at 2C after 100 cycles for batteries with a SF/SS separator, containing a 10 wt% of SS, which suggests a stabilizing effect of Sericin on discharge capacity. Further, a 50% and 35% of capacity of retention and capacity fade, respectively, is observed. The presented SF/SS membrane show high electrochemical stability, being suitable for implementation in a next generation of sustainable battery systems. This could allow the SS valorization considering that 150,000 tons of SS are abandoned each year, reducing the contamination of environmental effluents.

Temperature-Shift-Induced Mechanical Property Evolution of Lithium-Ion Battery Separator Using Cyclic Nanoindentation.

The evolution of mechanical properties of separators affected by temperature shifts is imperative for the performance of the lithium-ion battery. The flexible film characteristics hinder the evaluation of the micromechanical properties of separators. In the present study, considering the susceptibility of separators to temperature fluctuations, the temperature distribution of the battery during the discharging process at subzero temperature is obtained. Three sets of separator samples subjected to various temperature shifts are prepared. Through multicycle depth-sensitive nanoindentation, the temperature-dependent weakening of elastic modulus and hardness of separators is experimentally verified. Moreover, the variation trends of elastic modulus, hardness, and hysteresis response of the separator specimens in terms of temperature are investigated via extracting from the multicycle loading-unloading nanoindentation responses. The temperature-dependent variations in the elastic modulus of the separator were investigated by following heating, cooling, and thermostatic processes. Meanwhile, the indentation tests also verify that the effect of temperature shifts on the hardness exhibits an attenuation trend when heating or cooling is followed by a thermostatic process. The variation analysis of nanoindentation hardness as a function of temperature shifts shows typical size effects dependent on the nanoindentation depth. The temperature-induced residual stress and elemental distribution are also analyzed through characterization using X-ray diffraction and energy-dispersive X-ray spectroscopy, respectively. The obtained evolution law of temperature shift-induced mechanical properties of a separator could facilitate the optimal design of the separators and provide the supporting data to enhance the safety performance of lithium-ion batteries.

Pure cellulose lithium-ion battery separator with tunable pore size and improved working stability by cellulose nanofibrils.

Separator is a vital component of lithium-ion batteries (LIBs) due to its important roles in the safety and electrochemical performance of the batteries. Herein, we reported a cellulose nanofibrils (CNFs) reinforced pure cellulose paper (CCP) as a LIBs separator fabricated by a facile filtration process. The nanosized CNFs played crucial roles as a tuner to optimize the pore size of the as-prepared CCP, and also as a reinforcer to improve the mechanical strength of the resultant CCP. Results showed that the tensile strength of the CCP with 20 wt.% CNFs was 227 % higher compared to the commercial cellulose separator. In addition, the lithium cobalt oxide/lithium metal battery assembled with CCP separator displayed better cycle performance and working stability (capacity retention ratio of 91 % after 100 cycles) compared to the batteries with cellulose separator (52 %) and polypropylene separator (84 %) owing to the multiple synergies between CCP separator and electrolytes.

Single-Atom Coated Separator for Robust Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are strong contenders among lithium batteries due to superior capacity and energy density, but the polysulfide shuttling effect limits the cycle life and reduces energy efficiency due to a voltage gap between charge and discharge. Here, we demonstrate that graphene foam impregnated with single-atom catalysts (SACs) can be coated on a commercial polypropylene separator to catalyze polysulfide conversion, leading to a reduced voltage gap and a much improved cycle life. Also, among Fe/Co/Ni SACs, Fe SACs may be a better option to be used in Li-S systems. By deploying SACs in the battery separator, cycling stability improves hugely, especially considering relatively high sulfur loading and ultralow SAC contents. Even at a metal loading of ∼2 µg in the whole cell, an Fe SAC-modified separator delivers superior Li-S battery performance even at high sulfur loading (891.6 mAh g-1, 83.7% retention after 750 cycles at 0.5C). Our work further enriches and expands the application of SACs catalyzing polysulfide blocking and conversion and improving round trip efficiencies in batteries, without side effects such as electrolyte and electrode decomposition.

Recent Advances in Poly(vinylidene fluoride) and Its Copolymers for Lithium-Ion Battery Separators.

The separator membrane is an essential component of lithium-ion batteries, separating the anode and cathode, and controlling the number and mobility of the lithium ions. Among the polymer matrices most commonly investigated for battery separators are poly(vinylidene fluoride) (PVDF) and its copolymers poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and poly(vinylidene fluoride-cochlorotrifluoroethylene) (PVDF-CTFE), due to their excellent properties such as high polarity and the possibility of controlling the porosity of the materials through binary and ternary polymer/solvent systems, among others. This review presents the recent advances on battery separators based on PVDF and its copolymers for lithium-ion batteries. It is divided into the following sections: single polymer and co-polymers, surface modification, composites, and polymer blends. Further, a critical comparison between those membranes and other separator membranes is presented, as well as the future trends on this area.

Polyethylene Battery Separator as a Porous Support for Thin Film Composite Organic Solvent Nanofiltration Membranes.

Organic solvent nanofiltration (OSN) has made significant advances recently, and it is now possible to fabricate thin film composite (TFC) membranes with a selective layer thickness below 10 nm that gives ultrafast solvent permeance. However, such high permeance is inadvertently limited by the support membrane beneath the selective layer, and thus there is an urgent need to develop a suitable support to maximize TFC performance. In this work, we employed a commercially available polyethylene (PE) battery separator as a porous support to fabricate high performance TFC OSN membranes. To deposit a uniform polyamide selective layer onto the porous support via interfacial polymerization, the PE support was hydrophilized with O2 plasma and the reaction efficiency was optimized using a surfactant. Owing to the high surface porosity of the PE support and the high permselectivity of the PA layer, the PE-supported TFC membrane outperformed the previously reported OSN membranes and its performance exceeded the current performance upper bound. A solvent activation step dramatically improved the solvent permeance by 5-fold while maintaining nanoseparation properties. In addition to the superior OSN performance, the commercial availability of the PE support and simplified TFC fabrication protocol would make the PE-supported OSN membranes commercially attractive.

Silk Fibroin Separators: A Step Toward Lithium-Ion Batteries with Enhanced Sustainability.

Battery separators based on silk fibroin (SF) have been prepared aiming at improving the environmental issues of lithium-ion batteries. SF materials with three different morphologies were produced: membrane films (SF-F), sponges prepared by lyophilization (SF-L), and electrospun membranes (SF-E). The latter materials presented a suitable porous three-dimensional microstructure and were soaked with a 1 M LiPF6 electrolyte. The ionic conductivities for SF-L and SF-E were 1.00 and 0.32 mS cm-1 at 20 °C, respectively. A correlation between the fraction of ß-sheet conformations and the ionic conductivity was observed. The electrochemical performance of the SF-based materials was evaluated by incorporating them in cathodic half-cells with C-LiFePO4. The discharge capacities of SF-L and SF-E were 126 and 108 mA h g-1, respectively, at the C/2-rate and 99 and 54 mA h g-1, respectively, at the 2C-rate. Furthermore, the capacity retention and capacity fade of the SF-L membrane after 50 cycles at the 2C-rate were 72 and 5%, respectively. These electrochemical results show that a high percentage of ß-sheet conformations were of prime importance to guarantee excellent cycling performance. This work demonstrates that SF-based membranes are appropriate separators for the production of environmentally friendlier lithium-ion batteries.

Wetting behavior of four polar organic solvents containing one of three lithium salts on a lithium-ion-battery separator.

HYPOTHESIS: The wetting behavior of an electrolyte solution on the separator, determined by contact-angle measurements, has a significant effect on the internal resistance of the battery and on its cycle life. The solvent, the lithium-salt type and its concentration may affect the wettability. However, few systematic studies address the effect of salt concentration on surface tension and contact angle. EXPERIMENTS: Surface tensions and advancing contact angles were measured for dimethyl sulfoxide (DMSO), propylene carbonate (PC), dimethyl carbonate (DMC), and a PC/DMC mixture (1:1 mass ratio) with various concentrations of a lithium salt (LiClO4, LiPF6, and LiTFSI) at 23 °C. Measurements were made by a Krüss Drop Shape Analyzer 100, with a video camera mounted on a microscope to record the drop image. FINDINGS: For DMSO, PC and PC/DMC, surface tensions increase by adding LiClO4 or LiPF6 but decrease upon addition of LiTFSI. For DMC, the lithium salts have little impact on the surface tensions. For each solvent, contact angles and adhesion energies follow the same trend as those for surface tensions. The TFSI- anion reduces the surface tension of the solvent, favoring good wettability of the separator. The optimal surface tension for wettability of Celgard 2500 is at or below 26.1 mN/m.

Dendrite Suppression Membranes for Rechargeable Zinc Batteries.

Aqueous batteries with zinc metal anodes are promising alternatives to Li-ion batteries for grid storage because of their abundance and benefits in cost, safety, and nontoxicity. However, short cyclability due to zinc dendrite growth remains a major obstacle. Here, we report a cross-linked polyacrylonitrile (PAN)-based cation exchange membrane that is low cost and mechanically robust. Li2S3 reacts with PAN, simultaneously leading to cross-linking and formation of sulfur-containing functional groups. Hydrolysis of the membrane results in the formation of a membrane that achieves preferred cation transport and homogeneous ionic flux distribution. The separator is thin (30 µm-thick), almost 9 times stronger than hydrated Nafion, and made of low-cost materials. The membrane separator enables exceptionally long cyclability (>350 cycles) of Zn/Zn symmetric cells with low polarization and effective dendrite suppression. Our work demonstrates that the design of new separators is a fruitful pathway to enhancing the cyclability of aqueous batteries.

Porous cellulose diacetate-SiO2 composite coating on polyethylene separator for high-performance lithium-ion battery.

The developments of high-performance lithium ion battery are eager to the separators with high ionic conductivity and thermal stability. In this work, a new way to adjust the comprehensive properties of inorganic-organic composite separator was investigated. The cellulose diacetate (CDA)-SiO2 composite coating is beneficial for improving the electrolyte wettability and the thermal stability of separators. Interestingly, the pore structure of composite coating can be regulated by the weight ratio of SiO2 precursor tetraethoxysilane (TEOS) in the coating solution. The electronic performance of lithium ion batteries assembled with modified separators are improved compared with the pristine PE separator. When weight ratio of TEOS in the coating solution was 9.4%, the composite separator shows the best comprehensive performance. Compared with the pristine PE separator, its meltdown temperature and the break-elongation at elevated temperature increased. More importantly, the discharge capacity and the capacity retention improved significantly.

Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators.

We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.