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.     

A microporous gel electrolyte based on poly(vinylidene fluoride-co-hexafluoropropylene)/fully cyanoethylated cellulose derivative blend for lithium-ion battery

A gel polymer electrolyte based on the blend of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and fully cyanoethylated cellulose derivative (DH-4-CN) was prepared and characterized. Thermal, mechanical, swelling, liquid electrolyte retention and electrochemical properties, as well as microstructures of the prepared polymer electrolytes, were investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results showed that the addition of DH-4-CN could obviously improve the conductivity of PVDF-HFP based electrolyte. The maximum ionic conductivity of 4.36 mS cm⁻¹ at 20 °C can be obtained for PVDF-HFP/DH-4-CN 14:1 in the presence of 1 M LiPF₆ in EC and DMC (1:1, w/w). The dry blend membranes exhibit excellent thermal behavior. All the blend electrolytes are electrochemically stable up to about 4.8 V vs. Li/Li⁺ for all compositions. The results reveal that the composite polymer electrolyte qualifies as a potential application in lithium-ion battery.     

Electrochemical properties of Li ion polymer battery with gel polymer electrolyte based on polyurethane

Gel polymer electrolyte (GPE) was prepared using polyurethane acrylate as polymer host and its performance was evaluated. LiCoO₂/GPE/graphite cells were prepared and their electrochemical performance as a function of discharge currents and temperatures was evaluated. The precursor containing a 5 vol % curable mixture had a viscosity of 4.5 mPa s. The ionic conductivity of the GPE at 20 °C was about 4.5 × 10^–3 S cm^–1. The GPE was stable electrochemically up to a potential of 4.8 V vs Li/Li⁺. LiCoO₂/GPE/graphite cells showed a good high rate and low-temperature performance. The discharge capacity of the cell was stable with charge–discharge cycling.     

Chemically Modified Polyvinyl Butyral Polymer Membrane as a Gel Electrolyte for Lithium Ion Battery Applications

A novel porous membrane of chemically modified polyvinyl butyral (mPVB), with improved thermal properties and chemical stability for lithium ion battery applications, is successfully synthesized by utilizing the chain extension reaction of the OH units from PVB. The porous mPVB membranes are obtained via the tape casting and phase inversion method. The corresponding gel polymer electrolyte (GPE) is achieved by immersing the as‐prepared membranes in the liquid electrolyte. The electrochemical performances of the GPE show that the mPVB membranes have the features of good uniformity, high porosity ( ≈ 90%), great thermal stability, and high mechanical strength. Moreover, the GPE exhibits good chemical stability, a wide electrochemical window, as well as high ionic conductivity ( ≈ 1.21 × 10^?3 S cm^?1). A test of a Li/GPE/LiFePO₄ battery cell shows a capacity of 147.7 mAh g^?1 and excellent cycling stability, demonstrating the great potential of the mPVB‐based GPE for lithium ion battery applications.     

Preparation of gel polymer electrolytes using PMMA interpenetrating polymeric network and their electrochemical performances

A gel polymer electrolyte (GPE) is prepared from polymethylmethacrylate interpenetrating polymer network, benzoyl peroxide, and 1.1 M LiPF₆/EC-DEC (1:1 vol.%). The LiCoO₂/graphite cells are prepared and their electrochemical properties were evaluated at various current densities and temperatures. The viscosity of the precursor containing 5 vol.% curable mixture is around 4.6 mPa s. The ionic conductivity of the GPE at 20 °C is around 5.8×10⁻³ S cm⁻¹. The GPE has good electrochemical stability up to 4.8 V vs. Li/Li⁺. The capacity of the cell at 1.0C rate is 82% of the discharge capacity at 0.2C rate. The capacity of the cell at −10 °C is 86% of the discharge capacity at 20 °C. Discharge capacity of the cell with GPE is stable with charge-discharge cycling.     

Preparation of organic/inorganic hybrid semi-interpenetrating network polymer electrolytes based on poly(ethylene oxide-co-ethylene carbonate) for all-solid-state lithium batteries at elevated temperatures

Organic/inorganic hybrid semi-interpenetrating network (semi-IPN) polymer electrolytes (HIPEs) based on poly(ethylene oxide-co-ethylene carbonate) (PEOEC) have been developed for all-solid-state lithium battery applications. In comparison to those of poly(ethylene oxide) (PEO), salient features of the PEOEC are the amorphous nature and high dielectric constant, which provide enhanced ionic conductivity. The organic/inorganic hybrid network matrix in the HIPEs is composed of different contents of photo-cross-linked octa-functional POSS acrylate (OA-POSS) and ethoxylated trimethylolpropane triacrylate (ETPTA). The effect of OA-POSS on solid-state electrolyte properties of the HIPEs is investigated in terms of the dimensional stability, thermal behavior, and ionic conductivity. Due to the presence of the rigid and bulky POSS moiety, the HIPEs exhibit improvement in ionic conductivity along with enhanced dimensional stability. The high capacity and good cycle performance of lithium batteries with the HIPEs demonstrate feasibility of applying the HIPEs to solid-state electrolytes for all-solid-state lithium batteries that can operate at elevated temperatures.     

Dye-sensitized solar cells based on electrospun poly(vinylidenefluoride-co-hexafluoropropylene) nanofibers

Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers were prepared by the electrospinning method and used as polymer electrolytes in dye-sensitized solar cells (DSSCs). The electrolyte uptake and ionic conductivity of electrospun PVDF-HFP nanofibers with different diameters changed significantly, regardless of the nanofiber thickness. The PVDF-HFP nanofibers prepared from a 15 wt% spinning solution showed high ionic conductivity (1.295 S/cm) and electrolyte uptake (947 %). DSSCs based on the 15 wt% PVDF-HFP nanofiber electrolyte showed an electron transit time of 6.34 × 10^?3 s, electronic recombination time of 5.88 × 10^?2 s, and conversion efficiency of 3.13 %. Thus, we concluded that the electrospun PVDF-HFP nanofibers can be used as polymer electrolytes in flexible DSSCs as well.     

A novel lithium/sulfur battery based on sulfur/graphene nanosheet composite cathode and gel polymer electrolyte

A novel sulfur/graphene nanosheet (S/GNS) composite was prepared via a simple ball milling of sulfur with commercial multi-layer graphene nanosheet, followed by a heat treatment. High-resolution transmission and scanning electronic microscopy observations showed the formation of irregularly interlaced nanosheet-like structure consisting of graphene with uniform sulfur coating on its surface. The electrochemical properties of the resulting composite cathode were investigated in a lithium cell with a gel polymer electrolyte (GPE) prepared by trapping 1 mol dm⁻³ solution of lithium bistrifluoromethanesulfonamide in tetraethylene glycol dimethyl ether in a polymer matrix composed of poly(vinylidene fluoride-co-hexafluoropropylene)/poly(methylmethacrylate)/silicon dioxide (PVDF-HFP/PMMA/SiO₂). The GPE battery delivered reversible discharge capacities of 809 and 413 mAh g⁻¹ at the 1st and 50th cycles at 0.2C, respectively, along with a high coulombic efficiency over 50 cycles. This performance enhancement of the cell was attributed to the suppression of the polysulfide shuttle effect by a collective effect of S/GNS composite cathode and GPE, providing a higher sulfur utilization.     

Structure and properties of an organic rectorite/poly(methyl methacrylate) nanocomposite gel polymer electrolyte by in situ synthesis

The synthesis of organic‐modified rectorite (OREC)/polymethyl methacrylate (PMMA) nanocomposite gel polymer electrolyte (NGPE) via in situ polymerization was investigated using free radical initiator in an solution, in which organic plasticizer, propylene carbonate(PC) acted as a solvent. A serious of NGPE membranes with different OREC content were prepared and characterized. The dispersion and exfoliation statuses of the OREC in the prepared NGPE membranes were analyzed through X‐ray diffraction (XRD) and transmission electron microscope (TEM), and the results indicated that for the NGPE with 5 wt % OREC membrane, OREC was partly exfoliated and well dispersed in the gel polymer electrolyte system. The electrochemical properties of the NGPE were determined by alternating current (AC) impedance spectroscopy, which illustrated that the ionic conductivity of the nanocomposite gel polymer electrolyte firstly increased and then decreased with increasing OREC content. Meanwhile, the maximum value of ionic conductivity for nanocomposite gel polymer electrolytes was obtained when organic clay amount was 5 wt %. The interactions among the components of the NGPE were investigated by Fourier transform infrared (FTIR) spectroscopy. It was shown that there were specific interactions between OREC and the other components, which may influence the conductivity and the stability of GPEs. Finally, an thermal stability enhancement was presented by NGPE with 5 wt % OREC compared with GPE, which was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PMMA-[BMIM]PF_6-非质子溶剂复合型凝胶电解质的制备和性能

采用烯类单体MMA在离子液体[BMIM]PF6和PC、DMC等形成的混合溶液中聚合,合成一系列PMMA-[BMIM]PF6-非质子溶剂复合型凝胶电解质,并对其性能进行了研究。结果表明,当m([BMIM]PF6)∶m(PC)=45∶55时,凝胶电解质PMMA-PC-[BMIM]PF6的室温电导率值为3.44×10-3S/cm,当m([BMIM]PF6)∶m(DMC-PC)=35∶65时,PMMA-LiPF6-(PC-DMC)-[BMIM]PF6的室温电导率值为10.05×10-3S/cm,并随温度升高而增加,变化规律符合VTF方程。凝胶电解质热分解温度都在250℃以上,在80℃时热失重小于0.97%。锂离子的迁移数约为0.3。电化学窗口高达5.1V。     

A novel electrospun TPU/PVdF porous fibrous polymer electrolyte for lithium ion batteries

Novel blend-based gel polymer electrolyte (GPE) films of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) (denoted as TPU/PVdF) have been prepared by electrospinning. The electrospun thermoplastic polyurethane-co-poly (vinylidene fluoride) membranes were activated with a 1M solution of LiClO₄ in EC/PC and showed a high ionic conductivity about 1.6 mS cm⁻¹ at room temperature. The electrochemical stability is at 5.0 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. Cycling tests of Li/GPE/LiFePO4 cells showed the suitability of the electrospun membranes made of TPU/PVdF (80/20, w/w) for applications in lithium rechargeable batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

醋酸纤维素改性的P(VDF-HFP)-PEO基聚合物电解质的制备及性能研究

通过相转化法制备了一种由醋酸纤维素(CA)改性的P(VDF-HFP)-PEO聚合物隔膜,并将隔膜浸入锂盐溶液中得到凝胶态电解质(GPE)。通过扫描电子显微镜(SEM)、示差扫描量热分析仪(DSC)、热重分析仪(TGA)、交流阻抗仪、电化学工作站对隔膜及GPE的相关性能进行了表征测试。结果表明,CA改性后的聚合物隔膜相比改性前具有更好的孔结构、更优异的热学性能和吸液效果。这些特点赋予了GPE更高的离子电导率(室温下2.68×10^-3 S/cm),同时电化学窗口也达到4.25 V(vs.Li+/Li)。使用所制备的GPE组装电池进行测试,表现出了较好的放电容量和循环稳定性能。     

PVDF/TiO2/graphene oxide composite nanofiber membranes serving as separators in lithium-ion batteries

Improving the electrochemical properties of membranes in lithium-ion batteries (LIBs) is very important. Many attempts have been made to optimize ionic conductivity of membranes. The aim of this study was fabricating composite nanofiber membranes of poly(vinylidene fluoride) (PVDF), containing titanium dioxide (TiO₂) and graphene oxide (GO) nanoparticles to use in LIBs as separators. The morphology, crystallinity, porosity, pore size, electrolyte uptake, ionic conductivity, and electrochemical stability of the membranes were investigated using scanning electron microscopy, wide-angle X-ray diffraction, Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, and linear sweep voltammetry. The electrolyte uptake and ionic conductivity of the PVDF/TiO₂/GO composite nanofiber membranes containing 2 wt % GO were 494% and 4.87 mS cm⁻¹, respectively, which were higher than those of the other fabricated membranes as well as the commercial Celgard membrane. This could be attributed to the increased porosity, larger surface area, and higher amorphous regions of the PVDF/TiO₂/GO composite nanofiber membranes as a result of the synergistic effects of the nanoparticles. In this work, suitable optimized membranes with greater electrochemical stability compared with the other membranes were presented. Also, it was demonstrated that the incorporation of the TiO₂ and GO nanoparticles into the PVDF nanofiber membranes led to a porous structure where the electrolyte uptake enhanced. These properties made these membranes promising candidates for being used as separators in LIBs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48775.     

Nanocomposite polymer electrolytes for solid-state lithium-ion batteries with enhanced electrochemical properties

Solid-state polymer electrolytes (SPEs) have attracted significant attention owing to their improvement in high energy density and high safety performance. However, the low lithium-ion conductivity of SPEs at room temperature restricts their further application in lithium-ion batteries (LIBs). Herein, we propose a novel poly (ethylene oxide) (PEO)-based nanocomposite polymer electrolytes by blending boron-containing nanoparticles (BNs) in the PEO matrix (abbreviated as: PEO/BNs NPEs). The boron atom of BNs is sp²-hybridized and contains an empty p-orbital that can interact with the anion of lithium salt, promoting the dissociation of the lithium salts. In addition, the introduction of the BNs could reduce the crystallinity of PEO. And thus, the ionic conductivity of PEO/BNs NPEs could reach as high as 1.19 × 10⁻³ S cm⁻¹ at 60°C. Compared to the pure PEO solid polymer electrolyte (PEO SPEs), the PEO/BNs NPEs showed a wider electrochemical window (5.5 V) and larger lithium-ion migration number (0.43). In addition, the cells assembled with PEO/BNs NPEs exhibited good cycle performance with an initial discharge capacity of 142.5 mA h g⁻¹ and capacity retention of 87.7% after 200 cycles at 2 C (60°C).     

Gel Polymer Electrolyte with Anion‐Trapping Boron Moieties via One‐Step Synthesis for Symmetrical Supercapacitors

A novel gel polymer electrolyte (GPE) which is based on new synthesized boron‐containing monomer, benzyl methacrylate, 1 m LiClO₄/N,N‐dimethylformamidel liquid electrolyte solution is prepared through a one‐step synthesis method. The boron‐containing GPE (B‐GPE) not only displays excellent mechanical behavior, favorable thermal stability, but also exhibits an outstanding ionic conductivity of 2.33 mS cm^?1 at room temperature owing to the presence of anion‐trapping boron sites. The lithium ion transference in this gel polymer film at ambient temperature is 0.60. Furthermore, the symmetrical supercapacitor which is fabricated with B‐GPE as electrolyte and reduced graphene oxide as electrode demonstrates a broad potential window of 2.3 V. The specific capacitance of symmetrical B‐GPE supercapacitors retains 90% after 3000 charge–discharge cycles at current density of 1 A g^?1.     

Li+电池固态聚合物电解质研究进展

固态聚合物电解质具有高安全性、高成膜性和黏弹性等优点，并与电极具有良好的接触性和相容性，是实现高安全性和高能量密度固态Li⁺电池的重要电解质体系。然而聚合物电解质室温离子电导率较低（10^-8~10^-6 S·cm^-1），不能满足固态聚合物电池在常温运行的需求。因此，在提高离子电导率、机械强度和电化学稳定性等本征属性的基础上，同时探究改善电解质/电极的界面处及电极内部的离子输运是研发固态聚合物Li⁺电池面临的关键问题。主要从改性聚合物电解质用以提高Li⁺电池电化学性能的角度出发，综述了凝胶聚合物电解质、全固态聚合物电解质和复合固态电解质中的离子输运机制及其关键参数，总结了近年来聚合物电解质的最新研究进展和未来的发展方向。     

Designable air-stable and dendrite-free Li metal anode via the oligomer layer for in-situ gel polymer batteries

Lithium (Li) metal anode has been an indispensable electrode material in the development of the future battery system, especially in the pursuit of energy density of the solid state battery. However, the poor air stability and dendrite problems are stumbling blocks to the practical application of Li metal anode. Herein, we design the poly(methyl methacrylate) (PMMA) oligomer coating layer for the surface of Li metal anode (Li-PMMA). The Li-PMMA anode can obtain hydrophobic oxygen resistance ability and maintain air stability for 48h in the environment of 70% relative humidity. When applied to the liquid battery, the PMMA oligomer can open the double bond by the catalysis of Li⁺ and repolymerize into the PMMA gel polymer electrolyte (GPE). As a result, the cathode and anode are cohered together by GPE to become an in-situ GPE battery. The GPE displays high ionic conductivity (7.92 mS cm^-1) and perfect interfacial contact with various electrodes. The newly designed in-situ GPE is employed to Li||Li symmetric battery without separator, which can run up to 2000 h with the overpotential of only 2.8 mV. Applications of the in-situ GPE in Li-S battery and 5000mAh LiNi_0.5Co_0.2Mn_0.3O₂/Li pouch cell both obtain excellent electrochemical performance. Our strategy may provide a versatile and practical approach to promote the large-scale application for solid state Li metal batteries.     

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 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]     

Fabrication and properties of crosslinked poly(propylene carbonate maleate) gel polymer electrolyte for lithium‐ion battery

The poly(propylene carbonate maleate) (PPCMA) was synthesized by the terpolymerization of carbon dioxide, propylene oxide, and maleic anhydride. The PPCMA polymer can be readily crosslinked using dicumyl peroxide (DCP) as crosslinking agent and then actived by absorbing liquid electrolyte to fabricate a novel PPCMA gel polymer electrolyte for lithium‐ion battery. The thermal performance, electrolyte uptake, swelling ratio, ionic conductivity, and lithium ion transference number of the crosslinked PPCMA were then investigated. The results show that the T_g and the thermal stability increase, but the absorbing and swelling rates decrease with increasing DCP amount. The ionic conductivity of the PPCMA gel polymer electrolyte firstly increases and then decreases with increasing DCP ratio. The ionic conductivity of the PPCMA gel polymer electrolyte with 1.2 wt % of DCP reaches the maximum value of 8.43 × 10⁻³ S cm⁻¹ at room temperature and 1.42 × 10⁻² S cm⁻¹ at 50°C. The lithium ion transference number of PPCMA gel polymer electrolyte is 0.42. The charge/discharge tests of the Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3O₂ cell were evaluated at a current rate of 0.1C and in voltage range of 2.8–4.2 V at room temperature. The results show that the initial discharge capacity of Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3 O₂ cell is 115.3 mAh g⁻¹. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010