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Research Papers

Composite Nanofiber Membrane for Lithium-Ion Batteries Prepared by Electrostatic Spun/Spray Deposition OPEN ACCESS

[+] Author and Article Information
Bin Yu

School of Textile,
Tianjin Polytechnic University,
Tianjin 300387, China
e-mail: zijieyb@163.com

Xiao-Ming Zhao

Professor
School of Textile,
Tianjin Polytechnic University,
Tianjin 300387, China
e-mail: zhaoxiaoming@tjpu.edu.cn

Xiao-Ning Jiao

Professor
School of Textile,
Tianjin Polytechnic University,
Tianjin 300387, China
e-mail: xiaoningj@tjpu.edu.cn

Dong-Yue Qi

Guangzhou Fibre Product Testing
and Research Institute,
Guangzhou 511447, China
e-mail: qidongyue0403@163.com

1Corresponding author.

Manuscript received October 27, 2015; final manuscript received June 22, 2016; published online July 19, 2016. Assoc. Editor: Peter Pintauro.

J. Electrochem. En. Conv. Stor. 13(1), 011008 (Jul 19, 2016) (6 pages) Paper No: JEECS-15-1002; doi: 10.1115/1.4034030 History: Received October 27, 2015; Revised June 22, 2016

A new kind of sandwiched composite membrane (SCM) for lithium-ion batteries is prepared by depositing zirconia microparticle between two layers of electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) nanofibers by electrostatic spray deposition. The thermal shrinkage, electrochemical properties of the separator, and cycle performance for batteries with the SCM were investigated. The results show that the SCM has a high electrolyte uptake and easily absorbs electrolyte to form gelled polymer electrolytes (GPEs). The SCM GPEs have a high ionic conductivity of up to 2.06 × 10−3 S cm−1 at room temperature and show a high electrochemical stability potential of 5.4 V. With LiCoCO2 as cathode, the cell with SCM GPEs exhibits a high initial discharge capacity of 149.7 mAh g−1.

FIGURES IN THIS ARTICLE
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A battery constitutes of an anode, a cathode, and a separator; the separator provides the separation for ionic and electronic transport [1]. With the development of the lithium-ion battery industry, GPEs have a large potential application for use in lithium-ion batteries. The research on GPEs is mainly focused on their ionic conductivity dependence on temperature and good mechanical properties [2]. Up to date, several polymers used for GPEs have been investigated and developed. Fluoropolymers have received more attention because of their good electrochemical stability as well as their affinity to electrolyte solutions [37]. P(VdF-HFP) is the best choice for many researchers because the amorphous phase of hexafluoropropylene (HFP) helps to capture a large amount of liquid electrolytes; on the other hand, the crystalline phase of polyvinylidene fluoride (PVdF) acts as a mechanical support for the polymer matrix [810].

Electrospun fiber membrane is a novel separator for lithium-ion battery. The average diameter of electrospun fibers is at least 10–100 times thinner than that of conventional fibers produced by melt spinning [11]. The fibers with high specific surface area interconnect to form micropores, which can provide channels for the transmission of lithium ions and conduce to uptake more electrolyte solution [12]. Nevertheless, electrospun membranes as separators for lithium-ion batteries have poor mechanical properties. Thus, several methods are applied to ameliorate these properties: (i) the polymer with good performance acts as a matrix, and one or more polymers having complementary properties blend with matrix to produce membranes through electrospinning. Thus, a membrane with improved properties is gained because of the complementary roles of different polymers, such as P(VdF-HFP)/polymethyl methacrylate (PMMA), PVdF/polyacrylonitrile (PAN), and PVdF/polydiphenylamine [9,13,14]; (ii) a membrane with good mechanical properties acts as substrate, then a nanofiber layer deposits on the substrate via electrospinning [7,1517]; (iii) inorganic nanoparticles, such as SiO2, Al2O3, TiO2, or BaTiO3, were filled in polymer spinning solution to prepare an electrospun fiber membrane. The mechanical and electrochemical properties of the separator are better than that of separator without any filler [1821]; (iv) the separators made from polymers containing room temperature ionic liquids have a good electrochemical properties and excellent antithermal shrinkage performance [22,23]. In addition, properties of the nanofiber membrane can be improved through by heat treatment [24].

In this research, we report a novel SCM produced through electrostatic spun/spray deposition: the outer layers are electrospun P(VdF-HFP) fibers and the inner layer is ZrO2 inorganic particles deposited by electrostatic spray deposition. The electrochemical properties and antithermal stability of the separator were studied.

Materials.

P(VdF-HFP) was provided by Solvay Solexis, Inc., Tavaux, France, under the product name of SOLEF®21216/1001. Analytical grade N,N-Dimethyl formamide and acetone used as solvent were purchased from Tianjin Guangfu Chem. Co., Tianjin, China. ZrO2, with a particle of 20 nm, was supplied by Beijing Boyu New Materials Co., Beijing, China. LiPF6 electrolyte solution (1 mol dm−3) with the volume ratio of ethylene carbonate/ethyl methyl carbonate (1:3) was obtained from Tianjin Jinniu Power Source Materials Co., Tianjin, China. Commercial polyolefin based separator named Celgard 2400 with the thickness of 25 μm.

Membrane Preparation.

P(VdF-HFP) and ZrO2 nanoparticles were dried at 80 °C for 6 hrs before use. Homogeneous solution of P(VdF-HFP) with a concentration of 16 wt.% was prepared in the mixture of N,N-Dimethyl formamide and acetone (volume 7:3) by mechanical stirring. To prepare the dispersion of ZrO2 particle, prepare 50 g of P(VdF-HFP) solution with a concentration of 4 wt.%, into this solution, 6 g of ZrO2 particle was added under vigorous mechanical stirring to form uniform dispersion.

A layer of P(VdF-HFP) nanofiber membrane was first prepared through electrospinning with the solution of P(VdF-HFP), then a layer of ZrO2 particle was deposited by electrostatic spray deposition on the first nanofiber membrane, and another electrospun P(VdF-HFP) fiber film acts as the third layer forming a sandwiched composite membrane (SCM) of P(VdF-HFP)/ZrO2/P(VdF-HFP), as shown in Fig. 1. For comparison, a single-layer electrospun P(VdF-HFP) membrane (PHM) was prepared. The essential parameters of electrospinning and electrostatic spray deposition were as follows: applied voltage, 15 kV; distance between the syringe tip and collector, 20 cm; and feed rate, 0.8 mL/h. The time for electrospinning and electrostatic spray deposition was about 3 and 2.5 hrs, respectively. The thickness of the membrane was controlled ranging from 40 to 60 μm and the thickness of the layer of ZrO2 was about 3 μm. Then, the membranes were dried at room temperature for 24 hrs to prevent the shrinkage of the membranes before use.

Physical Characterization.

The morphologies of the composite membranes were examined by scanning electron microscopy (SEM, TM-1000, Japan). The air permeability of the membranes was expressed using Gurley values. The tensile tests were carried out on a universal testing machine model INSTRON 3369 and the sample size was 20 × 50 mm. The thermal shrinkage was determined by treating the membranes in an oven at 150 °C for 1 hr. The thermal shrinkage (A) was calculated by the following equation: Display Formula

(1)A(%)=(D0D1)/D0×100%

where D0 and D1 are the diameter of the membrane before and after heat treatment, respectively.

Liquid electrolyte uptake of the membranes was measured by immersing the membranes in the liquid electrolyte for 2 hrs. The excess surface solution was removed with wipes and the wet membranes were weighted quickly. The liquid electrolyte uptake (U) was evaluated by the following equation: Display Formula

(2)U=(W1W0)/W0×100%

where W0 and W1 are the mass of the dry and wet membranes, respectively.

Electrochemical Characterization.

The ionic conductivity of the liquid electrolyte-soaked membrane between two stainless-steel plate electrodes was examined by AC impedance analysis using an electrochemical workstation (CHI 660D, Beijing Huake Putian Technology Co., Beijing, China) over a frequency range of 1 Hz to 100 kHz at AC amplitude of 5 mV. The ionic conductively (σ) of the membranes was calculated by the following equation: Display Formula

(3)σ=d/(RS)

where d is the thickness of the GPEs, R is the bulk resistance, and S is the area of the symmetrical electrode.

The electrochemical stability of the liquid electrolyte-soaked membranes was evaluated by a linear sweep voltammetry using a three-electrode electrochemical cell consisting of nickel working electrode and a lithium reference and counter electrode at a scan rate of 10 mV s−1 [25].

Battery tests such as cycle property and rate capability were carried out in the voltage ranging from 2.8 to 4.2 V at room temperature using 2032 coin-type batteries consisting of LiCoO2 electrode as the cathode and lithium metal foil as the anode. Assembly of the batteries was carried out in an argon-filled glove box (Beijing Etelux Inertgas System Co., Ltd., Beijing, China). The charge/discharge curves and cycle properties of batteries were tested using a battery testing system (LX-PCBT-100-32D, Wuhan Lixing Power Co., Ltd., Wuhan, China). The batteries were cycled at a fixed charge/discharge current density of 0.1 C.

Physical Characterization of the Membrane.

Small pore-size and narrow pore-size distribution are significant properties of separators for lithium-ion battery. Cho found that ceramic powder can control pore size and pore-size distribution of the fiber membrane [7]. SEM micrographs of the cross section, outer layer, and inner layer of the SCM are shown in Fig. 2. It is clear that the SCM consists of three layers: the outer layers are electrospun P(VdF-HFP) fiber film and the inner layer consists of ZrO2 ceramic particles (continuous line in Fig. 2(a)). As shown in Fig. 2(b), P(VdF-HFP) fiber film has a porous structure composed of interconnected nanofiber layers with an average fiber diameter of about 1000 nm. The fiber film can absorb electrolyte solution and accept it into the membrane quickly. The diameter of the ZrO2 particles deposited by electrostatic spraying was about 3 μm, resulting from ZrO2 agglomerate property (Fig. 2(c)). P(VdF-HFP) acts as agglomerates to connect ceramic particles and, at the same time, forms micropores in favor of absorbing more electrolyte solution. However, the air permeability of composite membrane was reduced due to the existence of the inner film which increases the thickness of the SCM.

When immersed in the electrolyte solution, the PHM and SCM could uptake electrolyte quickly. About 2 hrs later, we founded that the PVDF-HFP fibers became swollen and formed gel state. The PHM changed into transparent GPEs, while, the SCM present white semi-GPEs due to the liquid electrolyte fills the porosity between the ceramic powders. The wet SCM has excellent morphological stability compared to the blank sample the PHM, which is conducive to assembly of battery. The physical properties of the membranes are listed in Table 1. In other research, electrospun fibrous membranes of composite of PVDF and PAN are prepared; the composite membrane with 25% PAN could uptake a high electrolyte uptake of more than 300% [11]. However, the electrolyte uptake of the SCM reaches up to 436%, which is 38.4% higher than that of the PHM. This is because the inner inorganic particle layer has a high porosity, which tends to absorb more electrolytes, and the outer swollen fiber film can fix the electrolyte.

The thermal stability of separator is an important factor which influences battery safety. However, the commercial separators for lithium-ion batteries are mostly polyolefin microporous membranes suffering from poor thermal shrinkage at high temperature [26]. It is reported that the thermal shrinkage of polypropylene-based membrane can reach 35% at 150 °C for 1 hr, which seriously affects the safety of the batteries when working in high temperature environments [27]. A photograph of the membranes, before and after thermal treatment at 150 °C for 1 hr, is presented in Fig. 3. It can be seen that the PHM displays curling and obvious shrinkage, while the SCM suffers almost no shrinkage. This is because the ZrO2 filled in the SCM has excellent thermal stability. When heat treated, the film of inorganic particles shows no change in dimensions, and inorganic particles can support the whole membrane to prevent shrinking. It is evident that the SCM has outstanding antithermal shrinkage property, which can avoid the likelihood to short-circuit, with a large area to enhance the safety of batteries.

Direct contact of the anode and the cathode can result in unwanted thermal runaway. Because of this, rupture or leak in the separator caused by the penetration of a conductive objects has to be avoided under any circumstances. Therefore, high mechanical resistance is one of the crucial separator properties for battery applications [28]. The stress–strain curves of the PHM, SCM, and Celgard 2400 were shown in Fig. 4. The tensile stress and elongation at break of the PHM, SCM, and Celgar 2400 were 7.9 MPa and 97.5%, 5.58 MPa and 80.45%, and 54.9 MPa and 39.7%, respectively. Compared with the commercial separator, the PHM and SCM had lower stress and higher elongation, which reflected the disadvantage of lower strength for electrospun membrane. In addition, the SCM had slight lower stress and elongation than the PHM, due to the presence of ZrO2 particle film affecting the membrane.

Electrochemical Properties.

Figure 5 presents the AC impedance data at room temperature for the SCM and PHM GPEs. Both of the oblique lines inclined toward the real axis indicting the electrode/electrolyte double-layer capacitance behaviors are obtained for all the samples over the whole range of frequencies tested [18]. The interception on z’-axis represents the bulk resistance (R) of the SCM and PHM GPEs. The ionic conductivity of the SCM GPE is 2.06 × 10−3 S cm−1, which is 74.6% higher than that of the PHM GPE. Compared with the PVDF/PMMA/PVDF sandwiched membrane reported, the ionic conductivity increases 6.7% [29]. This is due to: (i) the SCM can uptake more electrolyte compared to the PHM. Higher transmission rate of the lithium ion resulting from more electrolyte causes a high ionic conductivity [30]; (ii) the electrolyte absorbed in the inorganic particle film in the SCM almost presents liquid electrolyte, where the transmission of ions motion can be “free” [31]; (iii) the Lewis acid–base effect resulting from the interaction between polar groups on the surface of the inorganic particles and anion of electrolyte, which can weaken the interaction between the lithium ions and the negative charges, and contribute to the transmission of ions [32].

The temperature dependence of ionic conductivity of polymer electrolytes over the temperature ranges from 25 to 110 °C is shown in Fig. 6. The log σ versus T−1 curves of the electrolyte samples display a linear relationship, indicating that their conductive behavior follows Arrhenius equation. It is clear that the ionic conductivity of the GPEs increases with increasing temperature for both the SCM and PHM GPEs. The ionic conductivity of the polymer electrolyte is influenced by the number of carriers and the motion of the polymer molecular chain segments. Both of these factors will improve with increasing temperature; as a result, the ionic conductivity increases.

The results of electrochemical stability tests of the PHM and SCM GPEs by linear sweep voltammetry are shown in Fig. 7. When the voltage reaches a certain level, the decomposition reaction of electrode/electrolyte system occurs, and the voltage associated with the decomposition is the stable limit voltage for GPEs. It is found that no oxidation reaction occurred for both the GPE when the voltage is lower than 4.5 V. The electrochemical stability of the SCM GPE reaches up to 5.4 V, which is higher than that of the PHM GPE (4.6 V). The result is also better than other reports similar with this research [13,29]. This may be due to the interaction between Lewis acid sites on the anionic surface of ZrO2 particles and ClO4 (Lewis base), which slows down the decomposition of the lithium salt anion and enhances the electrochemical potential window [32]. The existence of ZrO2 particle film in the SCM can not only increase the electrolyte uptake but also improve the electrochemical stability. The results indicate that the SCM GPEs can meet the requirement for high-voltage lithium-ion batteries [3].

The initial charge/discharge cycle performance for batteries with the SCM and PHM is shown in Fig. 8. The batteries were charged up to 4.2 V under constant current-constant voltage mode, and then discharged to 2.8 V under constant current mode. The discharge capacities of batteries with the SCM, PHM, and Celgard 2400 are 149.7, 133.1, and 130.3 mAh g−1, respectively. Compared to the PHM GPE, the SCM delivers a higher specific capacity under the test conditions due to its larger liquid electrolyte up-taking. It is found that the coulombic efficiency of the battery with the SCM is higher than that of the battery with the PHM and Celgard 2400. During the first cycle, the irreversible reaction takes place between lithium metal and the electrolyte to form a layer of solid electrolyte interface (SEI). As reported in previous research, after adding ZrO2 into the microporous polymer electrolytes, no SEI formed on the electrode materials. As a result, the battery with the SCM has a higher coulombic efficiency [33].

The discharge capacity versus cycle number for the batteries subjected to 50 cycles is shown in Fig. 9. After 50 cycles, the discharge capacities of batteries with the SCM, PHM, and Celgard 2400 are 138.4, 105.1, and 108.5 mAh g−1; they retain 92.5%, 79.0%, and 83.3% of the initial discharge capacities, respectively. This is because the SCM can uptake more electrolyte to improve the electrochemical properties; on the other hand, ZrO2 particles can absorb water and HF produced in the process of charge/discharge, in the form of ZrF3·nH2O to slow down the decomposition of cathode materials.

In order to enhance the electrochemical properties of the electrospun PHM, an SCM was developed by depositing a layer of ZrO2 particles in two electrospun P(VdF-HFP) fiber `films by electrostatic spray deposition. The composite membrane has excellent electrolyte uptake, excellent electrochemical properties, and antithermal shrinkage. The ionic conductivity is 2.06 × 10−3 S cm−1, the electrolyte stability is up to about 5.4 V, the discharge capacity of the first cycle is 149.7 mAh g−1, and the thermal shrinkage is only 1.88% at 150 °C in air atmosphere for 1 hr. Therefore, the SCM shows great potential as separators for the lithium-ion batteries.

Nunes-Pereira, J. , Lopes, A. C. , Costa, C. M. , Rodrigues, L. C. , Silva, M. M. , and Lanceros-Méndez, S. , 2013, “ Microporous Membranes of NaY Zeolite/Poly(Vinylidene Fluoride–Trifluoroethylene) for Li-Ion Battery Separators,” J. Electroanal. Chem., 689(15), pp. 223–232. [CrossRef]
Ulaganathan, M. , Mathew, C. M. , and Rajendran, S. , 2013, “ Highly Porous Lithium-Ion Conducting Solvent-Free Poly(Vinylidene Fluoride-Co-Hexafluoropropylene)/Poly(Ethyl Methacrylate) Based Polymer Blend Electrolytes for Li Battery Applications,” Electrochim. Acta, 93(30), pp. 230–235. [CrossRef]
Li, H. , Chen, Y. , Ma, X. , Shi, J. , Zhu, B. , and Zhu, L. , 2011, “ Gel Polymer Electrolytes Based on Active PVDF Separator for Lithium Ion Battery. I: Preparation and Property of PVDF/Poly(Dimethylsiloxane) Blending Membrane,” J. Membr. Sci., 379(1–2), pp. 397–402. [CrossRef]
Raghavan, P. , Manuel, J. , Zhao, X. , Kim, D. , Ahn, J. , and Nah, C. , 2011, “ Preparation and Electrochemical Characterization of Gel Polymer Electrolyte Based on Electrospun Polyacrylonitrile Nonwoven Membranes for Lithium Batteries,” J. Power Sources, 196(16), pp. 6742–6749. [CrossRef]
Fisher, A. S. , Khalid, M. B. , Widstrom, M. , and Kofinas, P. , 2011, “ Solid Polymer Electrolytes With Sulfur Based Ionic Liquid for Lithium Batteries,” J. Power Sources, 196(22), pp. 9767–9773. [CrossRef]
Bansal, D. , Meyer, B. , and Salomon, M. , 2008, “ Gelled Membranes for Li and Li-Ion Batteries Prepared by Electrospinning,” J. Power Sources, 178(2), pp. 848–851. [CrossRef]
Cho, T. , Tanaka, M. , Ohnishi, H. , Kondo, Y. , Yoshikazu, M. , Nakamura, T. , and Sakai, T. , 2010, “ Composite Nonwoven Separator for Lithium-Ion Battery: Development and Characterization,” J. Power Sources, 195(13), pp. 4272–4277. [CrossRef]
Raghavan, P. , Zhao, X. , Manuel, J. , Chauhan, G. S. , Ahn, J. , Ryu, H. , Ahn, H. , Kim, K. , and Nah, C. , 2010, “ Electrochemical Performance of Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene)-Based Nanocomposite Polymer Electrolytes Incorporating Ceramic Fillers and Room Temperature Ionic Liquid,” Electrochim. Acta, 55(4), pp. 1347–1354. [CrossRef]
Ding, Y. , Zhang, P. , Long, Z. , Jiang, Y. , Xu, F. , and Di, W. , 2009, “ The Ionic Conductivity and Mechanical Property of Electrospun P(VdF-HFP)/PMMA Membranes for Lithium Ion Batteries,” J. Membr. Sci., 329(1–2), pp. 56–59. [CrossRef]
Li, Z. H. , Zhang, H. P. , Zhang, P. , Li, G. C. , Wu, Y. P. , and Zhou, X. D. , 2008, “ Effects of the Porous Structure on Conductivity of Nanocomposite Polymer Electrolyte for Lithium Ion Batteries,” J. Membr. Sci., 322(2), pp. 416–422. [CrossRef]
Gopalan, A. I. , Santhosh, P. , Manesh, K. M. , Nho, J. H. , Kim, S. H. , Hwang, C. , and Lee, K. , 2008, “ Development of Electrospun PVdF–PAN Membrane-Based Polymer Electrolytes for Lithium Batteries,” J. Membr. Sci., 325(2), pp. 683–690. [CrossRef]
Li, X. , Cheruvally, G. , Kim, J. , Choi, J. , Ahn, J. , Kim, K. , and Ahn, H. , 2007, “ Polymer Electrolytes Based on an Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene) Membrane for Lithium Batteries,” J. Power Sources, 167(2), pp. 491–498. [CrossRef]
Gopalan, A. I. , Lee, K. , Manesh, K. M. , and Santhosh, P. , 2008, “ Poly(Vinylidene Fluoride)–Polydiphenylamine Composite Electrospun Membrane as High-Performance Polymer Electrolyte for Lithium Batteries,” J. Membr. Sci., 318(1–2), pp. 422–428. [CrossRef]
Xi, J. , Qiu, X. , Li, J. , Tang, X. , Zhu, W. , and Chen, L. , 2006, “ PVDF–PEO Blends Based Microporous Polymer Electrolyte: Effect of PEO on Pore Configurations and Ionic Conductivity,” J. Power Sources, 157(1), pp. 501–506. [CrossRef]
Lee, Y. , Jeong, Y. B. , and Kim, D. , 2010, “ Cycling Performance of Lithium-Ion Batteries Assembled With a Hybrid Composite Membrane Prepared by an Electrospinning Method,” J. Power Sources, 195(18), pp. 6197–6201. [CrossRef]
Zhang, H. P. , Zhang, P. , Li, Z. H. , Sun, M. , Wu, Y. P. , and Wu, H. Q. , 2007, “ A Novel Sandwiched Membrane as Polymer Electrolyte for Lithium Ion Battery,” Electrochem. Commun., 9(7), pp. 1700–1703. [CrossRef]
Shin, W. , Lee, Y. , and Kim, D. , 2013, “ Hybrid Composite Membranes Based on Polyethylene Separator and Al2O3 Nanoparticles for Lithium-Ion Batteries,” J. Nanosci. Nanotechnol., 13(5), pp. 3705–3710. [CrossRef] [PubMed]
Kim, J. , Cheruvally, G. , Li, X. , Ahn, J. , Kim, K. , and Ahn, H. , 2008, “ Preparation and Electrochemical Characterization of Electrospun, Microporous Membrane-Based Composite Polymer Electrolytes for Lithium Batteries,” J. Power Sources, 178(2), pp. 815–820. [CrossRef]
Raghavan, P. , Zhao, X. , Kim, J. , Manuel, J. , Chauhan, G. S. , Ahn, J. , and Nah, C. , 2008, “ Ionic Conductivity and Electrochemical Properties of Nanocomposite Polymer Electrolytes Based on Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene) With Nano-Sized Ceramic Fillers,” Electrochim. Acta, 54(2), pp. 228–234. [CrossRef]
Raghavan, P. , Choi, J. , Ahn, J. , Cheruvally, G. , Chauhan, G. S. , Ahn, H. , and Nah, C. , 2008, “ Novel Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene)–In Situ SiO2 Composite Membrane-Based Polymer Electrolyte for Lithium Batteries,” J. Power Sources, 184(2), pp. 437–443. [CrossRef]
Huang, X. , 2013, “ Cellular Porous Polyvinylidene Fluoride Composite Membranes for Lithium-Ion Batteries,” J. Solid State Electrochem., 17(3), pp. 591–597. [CrossRef]
Kim, J. , Niedzicki, L. , Scheers, J. , Shin, C. , Lim, D. , Wieczorek, W. , Johansson, P. , Ahn, J. , Matic, A. , and Jacobsson, P. , 2013, “ Characterization of N-Butyl-N-Methyl-Pyrrolidinium Bis(Trifluoromethanesulfonyl)Imide-Based Polymer Electrolytes for High Safety Lithium Batteries,” J. Power Sources, 224(15), pp. 93–98. [CrossRef]
Liao, C. , Sun, X. , and Dai, S. , 2013, “ Crosslinked Gel Polymer Electrolytes Based on Polyethylene Glycol Methacrylate and Ionic Liquid for Lithium Ion Battery Applications,” Electrochim. Acta, 87(1), pp. 889–894. [CrossRef]
Gao, K. , Hu, X. , Dai, C. , and Yi, T. , 2006, “ Crystal Structures of Electrospun PVDF Membranes and Its Separator Application for Rechargeable Lithium Metal Cells,” Mater. Sci. Eng.: B, 131(1–3), pp. 100–105. [CrossRef]
Lee, S. W. , Choi, S. W. , Jo, S. M. , Chin, B. D. , Kim, D. Y. , and Lee, K. Y. , 2006, “ Electrochemical Properties and Cycle Performance of Electrospun Poly(Vinylidene Fluoride)-Based Fibrous Membrane Electrolytes for Li-Ion Polymer Battery,” J. Power Sources, 163(1), pp. 41–46. [CrossRef]
Liao, Y. , Sun, C. , Hu, S. , and Li, W. , 2013, “ Anti-Thermal Shrinkage Nanoparticles/Polymer and Ionic Liquid Based Gel Polymer Electrolyte for Lithium Ion Battery,” Electrochim. Acta, 89(1), pp. 461–468. [CrossRef]
Jiang, W. , Liu, Z. , Kong, Q. , Yao, J. , Zhang, C. , Han, P. , and Cui, G. , 2013, “ A High Temperature Operating Nanofibrous Polyimide Separator in Li-Ion Battery,” Solid State Ionics, 232(7), pp. 44–48. [CrossRef]
Plaimer, M. , Breitfuß, C. , Sinz, W. , Heindl, S. F. , Ellersdorfer, C. , Steffan, H. , Wilkening, M. , Hennige, V. , Tatschl, R. , Geier, A. , Schramm, C. , and Freunberger, S. A. , 2016, “ Evaluating the Trade-Off Between Mechanical and Electrochemical Performance of Separators for Lithium-Ion Batteries: Methodology and Application,” J. Power Sources, 306(29), pp. 702–710. [CrossRef]
Xiao, Q. , Li, Z. , Gao, D. , and Zhang, H. , 2009, “ A Novel Sandwiched Membrane as Polymer Electrolyte for Application in Lithium-Ion Battery,” J. Membr. Sci., 326(2), pp. 260–264. [CrossRef]
Lee, J. Y. , Lee, Y. M. , Bhattacharya, B. , Nho, Y. , and Park, J. , 2009, “ Separator Grafted With Siloxane by Electron Beam Irradiation for Lithium Secondary Batteries,” Electrochim. Acta, 54(18), pp. 4312–4315. [CrossRef]
Magistris, A. , Quartarone, E. , Mustarelli, P. , Saito, Y. , and Kataoka, H. , 2002, “ PVDF-Based Porous Polymer Electrolytes for Lithium Batteries,” Solid State Ionics, 152, pp. 347–354. [CrossRef]
Deka, M. , and Kumar, A. , 2011, “ Electrical and Electrochemical Studies of Poly(Vinylidene Fluoride)–Clay Nanocomposite Gel Polymer Electrolytes for Li-Ion Batteries,” J. Power Sources, 196(3), pp. 1358–1364. [CrossRef]
Subramania, A. , Sundaram, N. T. K. , Priya, A. R. S. , and Kumar, G. V. , 2007, “ Preparation of a Novel Composite Micro-Porous Polymer Electrolyte Membrane for High Performance Li-Ion Battery,” J. Membr. Sci., 294(1–2), pp. 8–15. [CrossRef]
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References

Nunes-Pereira, J. , Lopes, A. C. , Costa, C. M. , Rodrigues, L. C. , Silva, M. M. , and Lanceros-Méndez, S. , 2013, “ Microporous Membranes of NaY Zeolite/Poly(Vinylidene Fluoride–Trifluoroethylene) for Li-Ion Battery Separators,” J. Electroanal. Chem., 689(15), pp. 223–232. [CrossRef]
Ulaganathan, M. , Mathew, C. M. , and Rajendran, S. , 2013, “ Highly Porous Lithium-Ion Conducting Solvent-Free Poly(Vinylidene Fluoride-Co-Hexafluoropropylene)/Poly(Ethyl Methacrylate) Based Polymer Blend Electrolytes for Li Battery Applications,” Electrochim. Acta, 93(30), pp. 230–235. [CrossRef]
Li, H. , Chen, Y. , Ma, X. , Shi, J. , Zhu, B. , and Zhu, L. , 2011, “ Gel Polymer Electrolytes Based on Active PVDF Separator for Lithium Ion Battery. I: Preparation and Property of PVDF/Poly(Dimethylsiloxane) Blending Membrane,” J. Membr. Sci., 379(1–2), pp. 397–402. [CrossRef]
Raghavan, P. , Manuel, J. , Zhao, X. , Kim, D. , Ahn, J. , and Nah, C. , 2011, “ Preparation and Electrochemical Characterization of Gel Polymer Electrolyte Based on Electrospun Polyacrylonitrile Nonwoven Membranes for Lithium Batteries,” J. Power Sources, 196(16), pp. 6742–6749. [CrossRef]
Fisher, A. S. , Khalid, M. B. , Widstrom, M. , and Kofinas, P. , 2011, “ Solid Polymer Electrolytes With Sulfur Based Ionic Liquid for Lithium Batteries,” J. Power Sources, 196(22), pp. 9767–9773. [CrossRef]
Bansal, D. , Meyer, B. , and Salomon, M. , 2008, “ Gelled Membranes for Li and Li-Ion Batteries Prepared by Electrospinning,” J. Power Sources, 178(2), pp. 848–851. [CrossRef]
Cho, T. , Tanaka, M. , Ohnishi, H. , Kondo, Y. , Yoshikazu, M. , Nakamura, T. , and Sakai, T. , 2010, “ Composite Nonwoven Separator for Lithium-Ion Battery: Development and Characterization,” J. Power Sources, 195(13), pp. 4272–4277. [CrossRef]
Raghavan, P. , Zhao, X. , Manuel, J. , Chauhan, G. S. , Ahn, J. , Ryu, H. , Ahn, H. , Kim, K. , and Nah, C. , 2010, “ Electrochemical Performance of Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene)-Based Nanocomposite Polymer Electrolytes Incorporating Ceramic Fillers and Room Temperature Ionic Liquid,” Electrochim. Acta, 55(4), pp. 1347–1354. [CrossRef]
Ding, Y. , Zhang, P. , Long, Z. , Jiang, Y. , Xu, F. , and Di, W. , 2009, “ The Ionic Conductivity and Mechanical Property of Electrospun P(VdF-HFP)/PMMA Membranes for Lithium Ion Batteries,” J. Membr. Sci., 329(1–2), pp. 56–59. [CrossRef]
Li, Z. H. , Zhang, H. P. , Zhang, P. , Li, G. C. , Wu, Y. P. , and Zhou, X. D. , 2008, “ Effects of the Porous Structure on Conductivity of Nanocomposite Polymer Electrolyte for Lithium Ion Batteries,” J. Membr. Sci., 322(2), pp. 416–422. [CrossRef]
Gopalan, A. I. , Santhosh, P. , Manesh, K. M. , Nho, J. H. , Kim, S. H. , Hwang, C. , and Lee, K. , 2008, “ Development of Electrospun PVdF–PAN Membrane-Based Polymer Electrolytes for Lithium Batteries,” J. Membr. Sci., 325(2), pp. 683–690. [CrossRef]
Li, X. , Cheruvally, G. , Kim, J. , Choi, J. , Ahn, J. , Kim, K. , and Ahn, H. , 2007, “ Polymer Electrolytes Based on an Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene) Membrane for Lithium Batteries,” J. Power Sources, 167(2), pp. 491–498. [CrossRef]
Gopalan, A. I. , Lee, K. , Manesh, K. M. , and Santhosh, P. , 2008, “ Poly(Vinylidene Fluoride)–Polydiphenylamine Composite Electrospun Membrane as High-Performance Polymer Electrolyte for Lithium Batteries,” J. Membr. Sci., 318(1–2), pp. 422–428. [CrossRef]
Xi, J. , Qiu, X. , Li, J. , Tang, X. , Zhu, W. , and Chen, L. , 2006, “ PVDF–PEO Blends Based Microporous Polymer Electrolyte: Effect of PEO on Pore Configurations and Ionic Conductivity,” J. Power Sources, 157(1), pp. 501–506. [CrossRef]
Lee, Y. , Jeong, Y. B. , and Kim, D. , 2010, “ Cycling Performance of Lithium-Ion Batteries Assembled With a Hybrid Composite Membrane Prepared by an Electrospinning Method,” J. Power Sources, 195(18), pp. 6197–6201. [CrossRef]
Zhang, H. P. , Zhang, P. , Li, Z. H. , Sun, M. , Wu, Y. P. , and Wu, H. Q. , 2007, “ A Novel Sandwiched Membrane as Polymer Electrolyte for Lithium Ion Battery,” Electrochem. Commun., 9(7), pp. 1700–1703. [CrossRef]
Shin, W. , Lee, Y. , and Kim, D. , 2013, “ Hybrid Composite Membranes Based on Polyethylene Separator and Al2O3 Nanoparticles for Lithium-Ion Batteries,” J. Nanosci. Nanotechnol., 13(5), pp. 3705–3710. [CrossRef] [PubMed]
Kim, J. , Cheruvally, G. , Li, X. , Ahn, J. , Kim, K. , and Ahn, H. , 2008, “ Preparation and Electrochemical Characterization of Electrospun, Microporous Membrane-Based Composite Polymer Electrolytes for Lithium Batteries,” J. Power Sources, 178(2), pp. 815–820. [CrossRef]
Raghavan, P. , Zhao, X. , Kim, J. , Manuel, J. , Chauhan, G. S. , Ahn, J. , and Nah, C. , 2008, “ Ionic Conductivity and Electrochemical Properties of Nanocomposite Polymer Electrolytes Based on Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene) With Nano-Sized Ceramic Fillers,” Electrochim. Acta, 54(2), pp. 228–234. [CrossRef]
Raghavan, P. , Choi, J. , Ahn, J. , Cheruvally, G. , Chauhan, G. S. , Ahn, H. , and Nah, C. , 2008, “ Novel Electrospun Poly(Vinylidene Fluoride-Co-Hexafluoropropylene)–In Situ SiO2 Composite Membrane-Based Polymer Electrolyte for Lithium Batteries,” J. Power Sources, 184(2), pp. 437–443. [CrossRef]
Huang, X. , 2013, “ Cellular Porous Polyvinylidene Fluoride Composite Membranes for Lithium-Ion Batteries,” J. Solid State Electrochem., 17(3), pp. 591–597. [CrossRef]
Kim, J. , Niedzicki, L. , Scheers, J. , Shin, C. , Lim, D. , Wieczorek, W. , Johansson, P. , Ahn, J. , Matic, A. , and Jacobsson, P. , 2013, “ Characterization of N-Butyl-N-Methyl-Pyrrolidinium Bis(Trifluoromethanesulfonyl)Imide-Based Polymer Electrolytes for High Safety Lithium Batteries,” J. Power Sources, 224(15), pp. 93–98. [CrossRef]
Liao, C. , Sun, X. , and Dai, S. , 2013, “ Crosslinked Gel Polymer Electrolytes Based on Polyethylene Glycol Methacrylate and Ionic Liquid for Lithium Ion Battery Applications,” Electrochim. Acta, 87(1), pp. 889–894. [CrossRef]
Gao, K. , Hu, X. , Dai, C. , and Yi, T. , 2006, “ Crystal Structures of Electrospun PVDF Membranes and Its Separator Application for Rechargeable Lithium Metal Cells,” Mater. Sci. Eng.: B, 131(1–3), pp. 100–105. [CrossRef]
Lee, S. W. , Choi, S. W. , Jo, S. M. , Chin, B. D. , Kim, D. Y. , and Lee, K. Y. , 2006, “ Electrochemical Properties and Cycle Performance of Electrospun Poly(Vinylidene Fluoride)-Based Fibrous Membrane Electrolytes for Li-Ion Polymer Battery,” J. Power Sources, 163(1), pp. 41–46. [CrossRef]
Liao, Y. , Sun, C. , Hu, S. , and Li, W. , 2013, “ Anti-Thermal Shrinkage Nanoparticles/Polymer and Ionic Liquid Based Gel Polymer Electrolyte for Lithium Ion Battery,” Electrochim. Acta, 89(1), pp. 461–468. [CrossRef]
Jiang, W. , Liu, Z. , Kong, Q. , Yao, J. , Zhang, C. , Han, P. , and Cui, G. , 2013, “ A High Temperature Operating Nanofibrous Polyimide Separator in Li-Ion Battery,” Solid State Ionics, 232(7), pp. 44–48. [CrossRef]
Plaimer, M. , Breitfuß, C. , Sinz, W. , Heindl, S. F. , Ellersdorfer, C. , Steffan, H. , Wilkening, M. , Hennige, V. , Tatschl, R. , Geier, A. , Schramm, C. , and Freunberger, S. A. , 2016, “ Evaluating the Trade-Off Between Mechanical and Electrochemical Performance of Separators for Lithium-Ion Batteries: Methodology and Application,” J. Power Sources, 306(29), pp. 702–710. [CrossRef]
Xiao, Q. , Li, Z. , Gao, D. , and Zhang, H. , 2009, “ A Novel Sandwiched Membrane as Polymer Electrolyte for Application in Lithium-Ion Battery,” J. Membr. Sci., 326(2), pp. 260–264. [CrossRef]
Lee, J. Y. , Lee, Y. M. , Bhattacharya, B. , Nho, Y. , and Park, J. , 2009, “ Separator Grafted With Siloxane by Electron Beam Irradiation for Lithium Secondary Batteries,” Electrochim. Acta, 54(18), pp. 4312–4315. [CrossRef]
Magistris, A. , Quartarone, E. , Mustarelli, P. , Saito, Y. , and Kataoka, H. , 2002, “ PVDF-Based Porous Polymer Electrolytes for Lithium Batteries,” Solid State Ionics, 152, pp. 347–354. [CrossRef]
Deka, M. , and Kumar, A. , 2011, “ Electrical and Electrochemical Studies of Poly(Vinylidene Fluoride)–Clay Nanocomposite Gel Polymer Electrolytes for Li-Ion Batteries,” J. Power Sources, 196(3), pp. 1358–1364. [CrossRef]
Subramania, A. , Sundaram, N. T. K. , Priya, A. R. S. , and Kumar, G. V. , 2007, “ Preparation of a Novel Composite Micro-Porous Polymer Electrolyte Membrane for High Performance Li-Ion Battery,” J. Membr. Sci., 294(1–2), pp. 8–15. [CrossRef]

Figures

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Fig. 1

Preparation of the SCM

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Fig. 2

The SEM photographs of the composite membrane: (a) cross section, (b) outer layer, and (c) inner layer

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Fig. 3

The photograph of the membranes before and after thermal treatment

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Fig. 4

Stress–strain curves of the PHM, SCM, and Celgard 2400

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Fig. 5

Electrochemical impedance spectra of the SCM and PHM GPEs

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Fig. 6

Temperature-dependent ionic conductivity of the SCM and PHM GPEs

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Fig. 7

The electrochemical stability of SCM and PHM GPEs

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Fig. 8

Initial charge–discharge curves for the cells tested

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Fig. 9

Cycle performance for the cells tested

Tables

Table Grahic Jump Location
Table 1 The physical properties of the membranes

Errata

Discussions

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