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

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

Preparation and characterization of poly(vinylidene fluoride)-13X zeolite mixed matrix membranes for lithium ion batteries' separator with enhanced performance

13X zeolite was hydrothermally synthesized and poly(vinylidene fluoride) (PVDF)/13X zeolite particles mixed matrix membranes were prepared using phase inversion method as the lithium-ion battery separator. Hydrophilic and porous 13X zeolite loading impacts on the critical separator properties of morphology, wettability, electrolyte uptake, and high temperatures dimensional stability were investigated using scanning electron microscopy, contact angle, and thermal shrinkage analysis. Electrolyte uptake of the 13X zeolite particles loaded PVDF separators increased and also the incorporation facilitated the lithium ions migration (ion conductivity) due to the Lewis acidity of their structure. The 8 wt% 13X zeolite loaded separator (S2) revealed higher porosity (~+20%), electrolyte uptake (+80%), ion conductivity (+80%), and thermal shrinkage (~−47% at 165°C). C-rate capability and cycle performance of a cell battery assembled using the S2 separator considerably improved compared with those of the assembled by the neat PVDF and commercial polypropylene separators.     

Preparation and properties of gel‐filled PVDF separators for lithium ion cells

Polyether gel‐filled poly(vinylidene fluoride) separators (GF‐PVDF separators) were prepared by means of thermal crosslinking of poly(ethylene glycol) methyl ether acrylate (PEGMEA) and poly(ethylene glycol) diacrylate (PEGDA) as gel constituents. The intrinsic properties of GF‐PVDF and their corresponding gel polymer electrolyte (GPE) were characterized by SEM, DSC, and electrochemical methods. It was found a relatively better GPE could be got when the filled polyether content no more than 60 wt % and its ion conductivity could reach 1.3 × 10^?3 S cm^?1. The GPE is compatible with anode and cathode of lithium ion battery at high voltage and its electrochemical window is 4.6 V (vs. Li/Li⁺). The coulombic efficiency could reach 94% after 100 cycles for the cells using such GPE. The results reveal that the composite polymer electrolyte qualifies as a potential application in lithium cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44473.     

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

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

Preparation and properties of gel membrane containing porous PVDF-HFP matrix and cross-linked PEG for lithium ion conduction

Lithium ion conducting membranes are the key materials for lithium batteries. The lithium ion conducting gel polymer electrolyte membrane (Li-GPEM) based on porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix and cross-linked PEG network is prepared by a typical phase inversion process. By immersing the porous PVDF-HFP membrane in liquid electrolyte containing poly(ethylene glycol) diacrylate (PEGDA) and an initiator to absorb the liquid electrolyte at 25°C, and then thermally cross-linking at 60°C, the Li-GPEM is fabricated successfully. The measurements on its weight loss, mechanical and electrochemical properties reveal that the obtained Li-GPEM has better overall performance than the liquid and blend gel systems used as conductive media in lithium batteries. The ionic conductivity of the fabricated Li-GPEM can reach as high as 2.25 × 10^-3 S/cm at 25°C.     

Mitigating thermal runaway of lithium‐ion battery by using thermally sensitive polymer blend as cathode binder

Thermally sensitive binder (TSB) is developed as an internal safety mechanism of lithium‐ion battery (LIB). The TSB is a polymer blend of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP). Compared with regular PVDF binder, the softening and swelling of TSB are more pronounced when temperature is above 110 °C. With the TSB, the cycling performance of LIB cell is not affected; upon nail penetration, the heat generation rate is significantly reduced. The crystallinity of TSB is an important factor. This technology may lead to the development of thermal‐runaway‐mitigating LIB cells. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45737.     

Heat resistant microporous membranes based on soluble poly(aryl ether ketone) copolymers for lithium ion battery separator

To improve the safety and electrochemical properties of lithium ion batterie (LIB), a series of novel organic soluble poly(aryl ether ketone) (PAEK) copolymers were synthesized and used to fabricate LIB separators. The PAEK copolymers exhibited superior structural thermal stability and flame retardant, with glass transition temperature (T_g) above 150°C, oxygen index above 30 and no thermal decomposition before 500°C. Accordingly, the fabricated separators exhibited superior dimensional stability. The mechanical properties and electrolyte uptakes of the separators, as well as the electrochemical properties of the cells assembled with the separators were affected by the morphology and porosity of the separators. The separators with sponge-like structure exhibited less electrolyte uptakes but better mechanical properties than that of the ones with finger-like structure. The cell with finger-like structure separator exhibited poorer electrochemical properties than sponge-like structure separator, which might be caused by the collapse of some finger hole during the assemble process due to its poor mechanical properties. The charge–discharge performances of the cells after treated at 150°C demonstrates that the PAEK separators could be promising candidates for high-safety LIB.     

Shape stability enhancement of PVDF electrospun polymer electrolyte membranes blended with poly(2-acrylamido-2-methylpropanesulfonic acid lithium)

The purpose of this study is to overcome the poor dimensional stability of poly(vinylidene fluoride) (PVDF)-based electrospun membranes for polymer electrolytes, a new type of composite fibrous membranes based on PVDF/poly(2-acrylamido-2-methylpropanesulfonic acid lithium) (PAMPSLi) blend systems with different blend ratios were fabricated by electrospinning method. Morphology of the composite fibrous membranes was evaluated by scanning electron microscopy. Average diameters of the membranes were less than 250 nm, which were far less than that of pure PVDF fibrous membrane (400 nm). Fourier transform infrared spectroscopy and Raman scattering were used to characterize the interactions of two polymers. Wide-angle X-ray diffraction and differential scanning calorimetry techniques were applied to investigate the crystal structure of composite fibrous membranes. Owning to the good miscibility between PVDF and PAMPSLi, no phase-separated microstructure was observed in composite fibrous membranes. The membranes possessed a good wettability by liquid electrolytes and exhibited an excellent dimensional stability even at high loading of electrolytes. The polymer electrolyte showed the ionic conductivity of 3.45 × 10^?3 S/cm at room temperature and electrochemical stability up to 5.4 V for the blend ratio of 5/1. PVDF/PAMPSLi (5/1)-based polymer electrolyte was observed much more suitable than polymer electrolytes with other ratios of PVDF/PAMPSLi for application in high-performance lithium rechargeable batteries.     

Preparation and properties of gel membrane containing porous PVDF-HFP matrix and cross-linked PEG for lithium ion conduction

Lithium ion conducting membranes are the key materials for lithium batteries. The lithium ion conducting gel polymer electrolyte membrane (Li-GPEM) based on porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix and cross-linked PEG network is prepared by a typical phase inversion process. By immersing the porous PVDF-HFPmembrane in liquid electrolyte containing poly(ethylene glycol) diacrylate (PEGDA) and an initiator to absorb the liquid electrolyte at 25°C, and then thermally cross-linking at 60°C, the Li-GPEMis fabricated successfully. The measurements on its weight loss, mechanical and electrochemical properties reveal that the obtained Li-GPEM has better overall performance than the liquid and blend gel systems used as conductive media in lithium batteries. The ionic conductivity of the fabricated Li-GPEM can reach as high as 2.25 × 10⁻³ S/cm at 25°C. __________ Translated from Journal of Functional Materials, 2007, 38(2): 234–242 [译自: 功能材料]     

Sulfophenylated Poly (Ether Ether Ketone Ketone) Nanofiber Composite Separator with Excellent Electrochemical Performance and Dimensional Thermal Stability for Lithium-Ion Battery via Electrospinning

In this investigation, the sulfophenylated poly (ether ether ketone ketone) (SPEEKK) separators for lithium-ion batteries (LIBs) are prepared via electrospinning. The electrospun sulfophenylated poly (ether ether ketone ketone) membranes (es-SP) are then modified with lithium bis(trifuoro-methanesulfonyl)imide (LiTFSI) by immersing in the LiTFSI/ethanol solution to obtain the modified es-SP composite separators (es-SP-Li). SPEEKK displays excellent dimensional thermal stability, and thus the thermal shrinkage of es-SP-Li-20 (20% of LiTFSI in ethanol) composite separators is only 2% after 0.5 h at 200 °C. The strong polarity of sulfonic acid groups on SPEEKK and LiTFSI enhances the electrolyte wettability and uptake, and thus afford more Li source, so as to promote the conductivity of lithium ions in the composite separators, which in turn exhibit positive impacts on the rate and cycling stability performance of LIBs. The Li//LiFePO₄ cells assembled with es-SP-Li-20 separator demonstrate excellent electrochemical stability over 170 cycles at 0.2 C with a reversible discharge capacity of 153 mAh g⁻¹, and a promising rate capacity at 2 C. In short, the as-prepared es-SP-Li composite separators with excellent comprehensive property emerge as a promising application in LIBs.     

A phase separation method toward PPTA–polypropylene nanocomposite separator for safe lithium ion batteries

The building of separators with high thermal stability and security is important for lithium ion batteries. A novel, simple and successive process, which aims at coating poly‐p‐phenylene terephthamide (PPTA) onto commercial polypropylene (PP) separators, has been demonstrated. Without any additional binder, the PPTA nanofiber coating layer sticks to the porous PP separators by physical anchoring, endowing the composite separators with modified wettability toward electrolytes and heat resistance. Meanwhile, migration routes for lithium ions are guaranteed by the porous structure controlled by the self‐assembly of the fibrillar units during the nonsolvent induced phase separation. The cells equipped with the composite separators show better cycling performances. Moreover, the system based on the composite separators shows a sharp drop in ion conductivity after heat treatment at 200 °C for a certain period, indicating the shutdown effect of the composite separators, which can contribute to additional safety of lithium ion batteries. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 134, 46697     

Highly selective sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene)/poly(ether sulfone) blend proton exchange membranes for direct methanol fuel cells

Proton exchange membranes (PEMs) based on blends of poly(ether sulfone) (PES) and sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene) (sPVdF‐co‐HFP) were prepared successfully. Fabricated blend membranes showed favorable PEM characteristics such as reduced methanol permeability, high selectivity, and improved mechanical integrity. Additionally, these membranes afford comparable proton conductivity, good oxidative stability, moderate ion exchange capacity, and reasonable water uptake. To appraise PEM performance, blend membranes were characterized using techniques such as Fourier transform infrared spectroscopy, AC impedance spectroscopy; atomic force microscopy, and thermogravimetry. Addition of hydrophobic PES confines the swelling of the PEM and increases the ultimate tensile strength of the membrane. Proton conductivities of the blend membranes are about 10^?3 S cm^?1. Methanol permeability of 1.22 × 10^?7cm² s^?1 exhibited by the sPVdF‐co‐HFP/PES10 blend membrane is much lower than that of Nafion‐117. AFM studies divulged that the sPVdF‐co‐HFP/PES blend membranes have nodule like structure, which confirms the presence of hydrophilic domain. The observed results demonstrated that the sPVdF‐co‐HFP/PES blend membranes have promise for possible usage as a PEM in direct methanol fuel cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43907.     

Preparation of 4A zeolite coated polypropylene membrane for lithium-ion batteries separator

This study aims to improve wettability and thermal resistance of lithium-ion batteries separators. For this purpose, a commercial polypropylene (PP) separator was coated by 4A zeolite using poly(vinylidene fluoride) as binder and effects of the separators' zeolite content was investigated. All the coated separators showed lower contact angles, higher electrolyte uptakes, and less thermal shrinkages compared to the neat commercial separator. The coated PPA8 separator (zeolite to binder ratio of 8) showed the lowest wettability (contact angle of 0°) and electrolyte uptake (270%) due to its surface porosity resulting from the zeolite particles interstitial cavities as well as their internal cavities. Also, the PPA8 separator ion conductivity was found as 2.25 mS cm⁻¹ and C-rate and cycling performance of its assembled battery were higher compared to those of the commercial PP separator assembled battery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47841.     

Preparation and performance of aramid nanofiber membrane for separator of lithium ion battery

Stable and uniform dispersions of para‐aramid nanofibers have been prepared by adding methoxypolyethylene glycol (mPEG) in the polymerization process, followed by strong shear and dispersion. Aramid membranes are fabricated by vacuum‐assisted filtration of the nanofiber dispersion and assembled into batteries as separator. The membrane properties and battery performances are characterized in detail and the effect of mPEG content on these properties is explored. It is demonstrated that aramid membranes possess good electrolyte wettability, excellent mechanical properties, and superior thermal stability, which improve the safety of lithium ion batteries. The mPEG is critical to the formation of aramid nanofibers and improves the porosity and ionic conductivity of the membranes. These fascinating characteristics and facile papermaking method endow aramid membrane potential application as separator in lithium ion batteries with superior safety. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43623.     

Synthesis of porous Al2O3‐PVDF composite separators and their application in lithium‐ion batteries

In this article, a modified tape casting method is employed by dispersing and ball milling of Al₂O₃ powders in the poly (vinylidene fluoride) polymer, with the aim of developing uniform nanocomposite separators in the lithium‐ion cell system. The surface morphology, pore structure, heat‐resisting property, infrared property, and cell performance of the nanocomposite separators are investigated. The experimental results indicate that ball milling plays an important role in yielding homogeneous, porous nanocomposite separator membranes. The developed separator membranes exhibit high thermal stability and excellent electrochemical performance, therefore, are promising for use in the lithium‐ion cell systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2886–2890, 2013     

凝胶聚合物电解质的电化学性能

用化学交联法制备了凝胶聚合物电解质.聚烯烃多孔膜支撑的凝胶聚合物电解质具有优良的电化学性能, 室温电导率为1.01×10^-3S•cm^-1,锂离子迁移数为0.41,在Al电极上的氧化起始电位达到4.2 V以上.采用聚烯烃多孔膜支撑的凝胶聚合物电解质制备了聚合物锂离子电池,并研究了工艺条件对聚合物锂离子电池电化学性能的影响.研究的工艺条件包括：单体添加量和电极组合方式.优化后的聚合物锂离子电池具有良好的电化学性能,1 C放电容量为0.2 C放电容量的93.2%,经100次1 C循环后的剩余容量仍在80%以上.     

Bifunctional poly(ethylene glycol) based crosslinked network polymers as electrolytes for all‐solid‐state lithium ion batteries

Polymer electrolyte based lithium ion batteries represent a revolution in the battery community due to their intrinsic enhanced safety, and as a result polymer electrolytes have been proposed as a replacement for conventional liquid electrolytes. Herein, the preparation of a family of crosslinked network polymers as electrolytes via the ‘click‐chemistry’ technique involving thiol‐ene or thiol‐epoxy is reported. These network polymer electrolytes comprise bifunctional poly(ethylene glycol) as the lithium ion solvating polymer, pentaerythritol tetrakis (3‐mercaptopropionate) as the crosslinker and lithium bis(trifluoromethane)sulfonimide as the lithium salt. The crosslinked network polymer electrolytes obtained show low T_g, high ionic conductivity and a good lithium ion transference number (ca 0.56). In addition, the membrane demonstrated sterling mechanical robustness and high thermal stability. The advantages of the network polymer electrolytes in this study are their harmonious characteristics as solid electrolytes and the potential adaptability to improve performance by combining with inorganic fillers, ionic liquids or other materials. In addition, the simple formation of the network structures without high temperatures or light irradiation has enabled the practical large‐area fabrication and in situ fabrication on cathode electrodes. As a preliminary study, the prepared crosslinked network polymer materials were used as solid electrolytes in the elaboration of all‐solid‐state lithium metal battery prototypes with moderate charge–discharge profiles at different current densities leaving a good platform for further improvement. © 2018 Society of Chemical Industry     

Electrolyte‐resistant epoxy for bonding batteries based on sandwich structures

Adhesives that are stable in Li‐ion battery electrolytes are required to realize the potential of new battery designs that integrate structural elements with energy storage. Here, several polymers, commercial adhesives, and sealants were investigated to bond and seal a Li‐ion battery sandwich panel. Gravimetric electrolyte uptake measurements were compared with Hansen solubility parameters to predict long‐term durability of the materials exposed to battery electrolyte. The durability of adhesively bonded joints with an epoxy adhesive, which was selected as the lowest electrolyte uptake material, was examined using single lap shear strength tests and three‐point bending tests in a fabricated sandwich panel. The strength of the epoxy decreased after exposure to battery electrolyte due to solvent uptake in the bond. The addition of lithium hexafluorophosphate to the ethylene carbonate/dimethyl carbonate mixture severely decreased the strength with respect to the pure solvents. In device testing, the sandwich panel did not show any visible damage or leakage when loaded to above 1000 N during three‐point bending tests. Using sol extraction measurements and differential scanning calorimetry analyses, the optimized curing temperature for the epoxy adhesive ranged from 80 to 100 °C. At these temperatures, the cured adhesive had a highly crosslinked structure with low sol extraction. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46059.     

Fabrication and characterization of electrolyte membranes based on organoclay/tripropyleneglycol diacrylate/poly(vinylidene fluoride) electrospun nanofiber composites

Utilizing polymer electrospinning technology, novel electrolyte membranes based on poly(vinylidene fluoride) (PVDF)/organomodified clay (OC)/tripropyleneglycol diacrylate (TPGDA) composite nanofibers with a diameter of 100–400 nm were fabricated for application in lithium batteries. Ultraviolet photo‐polymerization of electrospun PVDF/OC/TPGDA nanofibers generated chemically crosslinked TPGDA‐grafted PVDF/OC nanofibers exhibiting robust mechanical and electrochemical properties. The prepared fibrous PVDF/OC/TPGDA electrolytes were characterized in terms of morphology, crystallinity, electrochemical stability, ionic conductivity and cell cycleability. Based on differential scanning calorimetry analysis, the crystallinity of PVDF decreased by ca 10% on employing the OC and TPGDA. Compared with pure PVDF film‐based electrolyte membranes, the TPGDA‐ and OC‐modified PVDF electrolyte membranes exhibited improved mechanical properties and various electrochemical properties. The OC‐ and TPGDA‐modified microporous membranes are promising candidates for overcoming the drawbacks of the lower mechanical stability of fibrous‐type electrolytes with further improvement of electrochemical performance. Copyright © 2009 Society of Chemical Industry     

Effect of hot‐press on electrospun poly(vinylidene fluoride) membranes

Poly(vinylidene fluoride) (PVDF) was electrospun into ultrafine fibrous membranes from its solutions in a mixture of N,N‐dimethylformamide and acetone (9:1, v/v). The electrospun membranes were subsequently treated by continuous hot‐press at elevated temperatures up to 155°C. Changes of morphology, crystallinity, porosity, liquid absorption, and mechanical properties of the membranes after hot‐press were investigated. Results of scanning electron microscopy showed that there were no significant changes in fibrous membrane morphology when the hot‐press temperature varied from room temperature to 130°C, but larger pores were formed because of fibers melting and bonding under higher temperatures. Analyses of X‐ray diffraction and differential scanning calorimeter exhibited that the crystalline form of PVDF could transfer from β‐type to α‐type during hot‐press at temperatures higher than 65°C. Tensile tests suggested that the mechanical properties of the electrospun PVDF membranes were remarkably enhanced from 25 to 130°C, whereas the porosity and the liquid absorption decreased. The hot‐press at 130°C was optimal for the electrospun PVDF membranes. The continuous hot‐press post‐treatment could be a feasible method to produce electrospun membranes, not limited to PVDF, with suitable mechanical properties as well as good porosity and liquid absorption for their applications in high‐quality filtrations or battery separators. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers