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Poly(Methyl Methacrylate) Reinforced Poly(Vinylidene Fluoride

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Poly(Methyl Methacrylate) Reinforced Poly(Vinylidene Fluoride Materials for Renewable and Sustainable Energy (2018) 7:5 https://doi.org/10.1007/s40243-018-0115-y ORIGINAL PAPER Poly(methyl methacrylate) reinforced poly(vinylidene fuoride) composites electrospun nanofbrous polymer electrolytes as potential separator for lithium ion batteries Yogita P. Mahant1 · Subhash B. Kondawar1 · Deoram V. Nandanwar2 · Pankaj Koinkar3 Received: 12 January 2018 / Accepted: 21 March 2018 / Published online: 27 March 2018 © The Author(s) 2018 Abstract Fabrication of nanofbrous polymer electrolyte membranes of poly(vinylidene fuoride) (PVdF) and poly(methyl meth- acrylate) (PMMA) in diferent proportion (PVdF:PMMA = 100:0, 80:20 and 50:50) by electrospinning is reported to inves- tigate the infuence of PMMA on lithium ion battery performance of PVdF membrane as separator. As-fabricated polymer electrospun nanofbrous membranes were characterized by SEM, FTIR, XRD, TGA and DSC for morphology, structure, crystallinity and thermal stability. PVdF–PMMA (50:50) polymer electrolyte membrane showed ionic conductivity 0.15 S/ cm and electrolyte uptake 290% at room temperature. After 50 cycles, the discharge capacity 140 mAh/g of Li/PE/LiFePO4 cells with PVdF–PMMA (50:50) as polymer electrolyte (PE) membrane was found to be retained around 93.3%. The elec- trolyte uptake, ionic conductivity, and discharge capacity retention were improved by optimizing the proportion of PMMA in PVdF. Nanofbrous PVdF–PMMA (50:50) polymer electrolyte membrane was found to be a potential separator for lithium ion batteries. Keywords Poly(vinylidene fuoride) · Poly(methyl methacrylate) · Polymer electrolyte · Electrospinning · Nanofbers · Lithium ion batteries Introduction polymer electrolyte [1–6]. Poly(ethylene oxide) (PEO), poly- acrylonitrile (PAN), poly(methyl methacrylate) (PMMA), Lithium ion batteries have been improved using polymer poly(vinylidene fluoride) (PVDF), poly(vinyl alcohol) nanofbrous electrolyte membrane with its highly porous (PVA) and poly(vinylidene fuoride-co-hexafuoropropylene) structure, high electrolyte uptake and ionic conductivity (PVDF–HFP) have been studied as host polymer for fabri- to transport as much as lithium ions through it. Polymer cating nanofbrous polymer electrolyte membrane [7–16]. nanofbrous electrolyte membrane provides wide electro- Among these polymers, poly(vinylidene fuoride) (PVdF) chemical operating window and good thermal stability use- has been mostly used as a semi-crystalline polymer with ful to prevent electrolyte leakage and to minimize the fring excellent flm-forming ability, high dielectric constant and hazard for high safety of batteries as compared to liquid thermal stability [17]. But the crystalline domains of PVdF restrict the penetration of liquid electrolytes and the move- ment of lithium ions from between the electrodes during * Subhash B. Kondawar charging and discharging which show low ionic conductiv- [email protected] ity. Therefore, researchers in this feld are more engaged * Pankaj Koinkar to prepare polymer electrolyte membranes by blending or koinkar@tokushima‑u.ac.jp forming composites using diferent polymers or metal oxides 1 Department of Physics, Rashtrasant Tukadoji Maharaj to increase ionic conductivity, electrolyte uptake, and elec- Nagpur University, Nagpur 440033, India trochemical stability than that of pure polymer electrolytes 2 Department of Physics, Shri Mathuradas Mohata College [18–22]. Li et al. prepared PVDF/PMMA membrane by of Science, Nagpur 440023, India anchoring PMMA to multiporous PVDF surface via elec- 3 Department of Optical Science, Tokushima University, tron beam preirradiation grafting technique and showed −3 Tokushima 7708506, Japan ionic conductivity 6.1 × 10 S/cm [23]. Also, Idris et al. Vol.:(0123456789)1 3 5 Page 2 of 9 Materials for Renewable and Sustainable Energy (2018) 7:5 1 3 Materials for Renewable and Sustainable Energy (2018) 7:5 Page 3 of 9 5 ◂Fig. 1 a SEM image of electrospun PVdF nanofbrous membrane. b was dissolved in a mixed solvent N,N-dimethylformamide SEM image of electrospun PVdF–PMMA (80:20) nanofbrous mem- (DMF)/tetrahydrofuran (THF) (7:3, V/V) and magnetically brane. SEM image of electrospun PVdF–PMMA (50:50) nanof- c stirred to form a homogeneous solution and then trans- brous membrane. d Histogram of electrospun PVdF nanofbrous membrane. e Histogram of electrospun PVdF–PMMA (80:20) nanof- ferred the mixed polymer solution to disposable syringe brous membrane. f Histogram of electrospun PVdF–PMMA (50:50) for electrospinning to get continuous nanofbers. During nanofbrous membrane electrospinning, computer controlled fow rate 0.6 ml/h, electric field 20 kV and distance 18 cm between the prepared PVdF/PMMA microporous membranes using syringe needle and grounded collector (aluminum foil) the phase-separation method with increasing percentage were maintained. The nanofbrous membrane on the col- of PMMA and showed discharge capacity of 133 mAh/g lector plate was dried under vacuum at 70 °C for 12 h and [24]. Many diferent synthesis methods are used to prepare then separated from the foil for preparation of polymer polymer electrolyte membrane by solution casting [15, 20], electrolyte. In the similar way, PVdF–PMMA (50:50) and phase inversion [25] and electrospinning [26]. Among them, PVdF–PMMA (100:00) abbreviated as pure PVdF have electrospinning is a simple method for preparation of nanof- been prepared by electrospinning with the same operating brous membranes with high porosity due to tunable fber conditions. PVdF–PMMA nanofbrous polymer electro- diameter controlled by varying applied electric feld, dis- lytes were prepared by immersing the electrospun nanof- tance between syringe needle and grounded collector, poly- brous membranes in 1 M LiPF 6 (lithium hexafurophos- mer solution concentration, and fow rate of viscous polymer phate) in EC:DMC (1:1 v/v) (ethylene carbonate and solution. Porosity is the size-dependent property; therefore, dimethyl carbonate) solution at room temperature in a electrospun nanofbers of blended polymers synthesized by glove box under nitrogen atmosphere. electrospinning possess high porosity which is responsible for increase in electrolyte uptake and high ionic conductiv- ity at room temperature [27, 28]. Li et al. and Mahant et al. Characterizations prepared fbrous membranes of poly(vinylidene fuoride)/ poly(methyl methacrylate) (PVdF/PMMA) by electrospin- The surface morphology of electrospun nanofbrous mem- ning method and showed ionic conductivity 3.5 × 10−3 and branes was investigated by scanning electron microscope 2.95 × 10−3 S/cm, respectively [29, 30]. Therefore, eforts (CARL ZEISS EVO-18). Fourier transform infrared have been made to optimize the composition of PVdF and (FTIR) spectra of electrospun nanofbrous membranes PMMA to fabricate their composites nanofbrous membrane were obtained on α-Bruker model. X-ray diffraction by electrospinning so as to increase the ionic conductivity. (XRD) patterns of electrospun nanofbrous membranes In this work, the fabrication of polymer nanofibrous were on Rigaku Minifex II Desktop X-ray difractometer. electrolyte membranes of PVdF–PMMA composites in dif- The crystallinity of electrospun nanofbrous membranes ferent proportion (PVdF:PMMA = 100:0, 80:20 and 50:50) was obtained using differential scanning calorimetry by electrospinning is reported to investigate the infuence (DSC) (Mettler Toleno DSC 822 e) with heating rate 10 °C of PMMA on lithium ion battery performance. The efect per min under N2 atmosphere. Thermogravimetric analysis of concentration of PMMA in composites on morphology, (TGA) was done by Perkin Elmer STA 6000 at the heat- ionic conductivity, porosity and discharge capacity retention ing rate 10 °C min −1 from room temperature to 700 °C for lithium ion battery separator is studied and systemati- under N2 atmosphere. Porosity of electrospun nanofbrous cally compared. membranes was calculated by weighing membrane before and after absorbing n-butanol and knowing the density of n-butanol. The electrolyte uptake of polymer electrolyte Experimental membranes was calculated by soaking the membrane in lithium hexafurophosphate (LiPF 6), ethylene carbonate Preparation of PVdF–PMMA composites nanofbrous (EC) and dimethyl carbonate (DMC) solution. The ionic polymer electrolytes conductivity ( ) of polymer electrolyte membranes was determined through an ionic conductivity cell, by sand- PVdF–PMMA composites were prepared with varying wiching a given polymer electrolyte membrane between weight ratio of PMMA in PVdF. The total polymer con- two stainless steel blocking electrodes (SS/polymer elec- centration was fxed at 15 wt%. PVdF–PMMA composites trolyte membrane/SS, SS: stainless steel) using Zahner nanofbrous membranes in diferent proportion of PVdF Zennium Electrochemical Analyzer at room temperature and PMMA were prepared by electrospinning. In a typical in frequency range between 10 mHz and 100 kHz with AC procedure for the preparation of PVdF–PMMA (50:50) amplitude of 10 mV. nanofbrous membrane, 15% PVdF–PMMA (5:5, w/w) 1 3 5 Page 4 of 9 Materials for Renewable and Sustainable Energy (2018) 7:5 Results and discussion assigned to stretching vibration of C=C. The band at −1 1401 cm is related to stretching vibration of CF 2 group. −1 Figure 1 shows SEM images and histograms of electrospun The bands appearing at 1077 and 1005 cm are appeared (a) PVdF, (b) PVdF/PMMA (80–20), and (c) PVdF–PMMA due to scissoring vibration of CF2 group and stretching −1 (50–50) nanofbrous membranes. It can be seen from SEM vibration
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