DOCSLIB.ORG

Preparation and Characterization of PAN–KI Complexed Gel Polymer Electrolytes for Solid-State Battery Applications

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Preparation and Characterization of PAN–KI Complexed Gel Polymer Electrolytes for Solid-State Battery Applications Bull. Mater. Sci., Vol. 39, No. 4, August 2016, pp. 1047–1055. c Indian Academy of Sciences. DOI 10.1007/s12034-016-1241-8 Preparation and characterization of PAN–KI complexed gel polymer electrolytes for solid-state battery applications N KRISHNA JYOTHI1,2, K K VENKATARATNAM3, P NARAYANA MURTY2 and K VIJAYA KUMAR1,∗ 1Solid State Ionics Research Laboratory, Department of Physics, K L University, Vaddeswaram 522502, India 2Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522510, India 3Department of Physics, Malaviya National Institute of Technology Jaipur, Jaipur 302017, India MS received 4 July 2015; accepted 16 February 2016 Abstract. The free standing and dimensionally stable gel polymer electrolyte films of polyacrylonitrile (PAN): potassium iodide (KI) of different compositions, using ethylene carbonate as a plasticizer and dimethyl formamide as solvent, are prepared by adopting ‘solution casting technique’ and these films are examined for their conductivi- ties. The structural, miscibility and the chemical rapport between PAN and KI are investigated using X-ray diffrac- tion, Fourier transform infrared spectroscopy and differential scanning calorimetry methods. The conductivity is enhanced with the increase in KI concentration and temperature. The maximum conductivity at 30◦C is found to be 2.089 × 10−5 Scm−1 for PAN:KI (70:30) wt%, which is nine orders greater than that of pure PAN (<10−14 Scm−1). The conductivity-temperature dependence of these polymer electrolyte films obeys Arrhenius behaviour with activa- tion energy ranging from 0.358 to 0.478 eV. The conducting carriers of charge transport in these polymer electrolyte films are identified by Wagner’s polarization technique and it is found that the charge transport is predominantly due to ions. The better conducting sample is used to fabricate the battery with configuration K/PAN + KI/I2+ C + electrolyte and good discharge characteristics of battery are observed. Keywords. Polyacrylonitrile; solution casting technique; differential scanning calorimetry; X-ray diffraction; electrical properties. 1. Introduction The smoothness of this metal makes it easier for the compo- nents of the battery to have good contact to accomplish and Recently a lot of attention has been paid to the research acti- keep contact with other components in the battery. Moreover, vities of developing gel polymer electrolytes for solid-state potassium is more moisture resistant than lithium [13]. battery applications with good conductivity. In view of the Compared with the other polymers, PAN-based elec- above fact that solid-state battery has many advantages, trolytes have been extensively studied because of their good such as higher energy density, solvent-free condition, leak chemical, flame resistance and electrochemical stability proof, easy process ability and light weight [1–5]. Several [14–17]. PAN is one of the most important fibre-forming poly- earlier studies in this field are focused upon polyethylene mers and is widely used because of its high strength, abra- oxide (PEO), polyvinyl alcohol, polyvinyl pyrrolidone (PVP) sion resistance and good insect resistance [18]. It is used to and polyacrylonitrile (PAN) complexed with NaI, NaClO3, produce a large variety of products, including ultrafiltration NaYF4, KYF4 and LiCF3SO3 [6–12]. Although very few membranes, hollow fibres for reverse osmosis, fibres for tex- investigations are conducted on potassium complexed poly- tiles, oxidized flame retardant fibres like PANOX and carbon mer electrolytes, still no attention is paid on potassium salt fibre. Although the conductivity of pristine PAN is less than complexed PAN-based polymer electrolytes. 10−14 Scm−1, this static problem confine its further applications. Lithium batteries have advantages such as high energy PAN is usually synthesized using free radical polymer- density and rechargeability, which make them commercially ization. Generally it forms copolymers with acrylonitrile, active. Despite their advantages, they experience the ill effects methyl acrylate, acrylonitrile and methyl methacrylate. PAN of operational limitations, for example, high cost, trouble in has a glass transition point of about 107◦C and melting point taking care of atmospheric conditions due to high reactiv- of about 319◦C, and it decomposes at this temperature [19]. ity. So, the research has been focused on potassium salts due To enhance the conductivity of polymer electrolytes, sev- to their several advantages over lithium counterparts. Potas- eral techniques are suggested in the literature, including sium is less expensive and much more abundant than lithium. the use of blend polymers, addition of a ceramic filler, plasticizers and radiation. Two plasticizing solvents ethylene carbonate (EC) and dimethyl formamide (DMF) are chosen ∗Author for correspondence ([email protected]) as solvents in this study. EC has high dielectric constant and 1047 1048 N Krishna Jyothi et al low viscosity, which weakens the columbic force between DSC, TA Instruments, at a heating rate of 10◦Cmin−1 under cation and anion of the salt. Consequently, salt separation nitrogen atmosphere in the temperature range of 40–350◦C. takes place. Further, plasticizers decrease the glass transi- tion temperature of the polymer electrolyte and accordingly enhance the segmental motion of the polymer backbone and 2.4 Electrical studies create free volume. Therefore, the ions can migrate easily through the void, as a result ionic conductivity increases [20]. 2.4a Conductivity measurements: For conductivity mea- In the present work, we have developed and study the elec- surements, circular discs of diameter 2 cm were cut from the trical properties of PAN-based KI complexed gel polymer films. A disc sample was sandwiched between a pair of silver electrolytes and verify their potential in solid-state battery electrodes and spring loaded into a sample holder of lab- applications. made conductivity setup [21]. Room temperature conductivi- ties of films were measured using HIOKI 3532-50 LCR Hitester in 50 Hz to 5 MHz frequency range. 2. Experimental 2.1 Materials 2.4b Transport properties: Wagner’s polarization method was carried out at room temperature on disc-shaped samples, Polyacrylonitrile (PAN; MW = 1,50,000 g mol−1), ethy- which were sandwiched between silver electrodes. Polariza- lene carbonate (EC) were from Sigma Aldrich and potas- tion current was measured with respect to time in response sium iodide (KI), dimethyl formamide (DMF) were from to an applied DC bias of 1.5 V. Ionic transport (tion) and Merck. All reagents were used, as received, without further electronic transport (tele) numbers were calculated using the purification. graph of polarization current vs. time. 2.2 Preparation of the gel polymer electrolyte films 2.4c Fabrication of polymer battery: Potassium polymer battery was fabricated by sandwiching the salt complexed Solution casting technique was used to prepare gel polymer film as electrolyte between anode and cathode pellets electrolyte films. In this method, KI was first dissolved in the with the arrangement [K (anode)/(PAN + KI) (polymer mixture of EC and DMF with continuous stirring at 60◦Cfor electrolyte)/(I2 + C + electrolyte) (cathode)]. This entire 12 h. Then the polymer PAN was mixed with the prepared assembly was finally covered in the sample holder. In this solution and the mixture was stirred up to 36 h to obtain a battery, potassium metal was used as the anode (negative homogeneous solution. Subsequently, the prepared solution electrode). For the preparation of cathode, an accurate mix- was poured into polypropylene Petri dishes and evaporated ture of iodine (I2), graphite (C) and the electrolyte material slowly at room temperature under vacuum until the gel film in the wt% of 5:5:1, respectively, was obtained by mechani- was formed. The polymer electrolyte samples were trans- cal grinding. It was pressed in the form of pellet at a pressure ferred into desiccators for further drying before the test. The of 200 MPa after proper mixing of constituents. The battery films formed were mechanically stable, transparent and free parameters, short circuit current (SCC), open circuit voltage standing with thickness range of 150 μm. (OCV), current density, energy density, power density and discharge time were evaluated. 2.3 Structural characterizations 2.3a X-ray diffraction: To investigate the structure of the 3. Results and discussion gel polymer electrolyte films, X-ray diffraction (XRD) spec- tra were carried out using an X’pert diffractometer (Philips 3.1 XRD analysis PANalytical) with CuKα radiation (λ = 1.5403 A),˙ and the diffraction patterns were recorded for 2θ values between 10◦ XRD measurements are performed on PAN-based KI com- and 90◦. plexed films to examine the crystallinity and the amorphous nature of the films. Figure 1 is a comparative study of the XRD patterns of pure PAN and PAN doped with different 2.3b Fourier transform infrared spectroscopy: Fourier KI concentration regions. The comparative study shows that transform infrared (FTIR) absorption spectra were recorded the intensity of the crystalline peak of PAN decreases grad- with the help of the Perkin Elmer FTIR spectrometer (Spec- ually with the addition of KI salt (up to 30 wt%) to the trum II USA) in the wavenumber range of 450–4000 cm−1 polymer, significant decrease in the degree of crystallinity with spectral resolution of 2 cm−1. of the electrolyte films. It may be due to the disturbance in the semicrystalline structure of the film by an addition of KI 2.3c Differential scanning calorimetry: The glass transition salt. The XRD pattern of the pure PAN film shows a crys- ◦ temperature (Tg) and melting temperature (Tm) of the gel poly- talline peak at 2θ = 17 , corresponding to orthorhombic mer electrolyte films were determined using an Auto Q20 PAN (110) reflection [22]. The XRD patterns show that the PAN–KI complexed gel polymer electrolytes 1049 Figure 1. X-ray diffraction patterns of pure PAN, pure KI salt and PAN:KI complexed films. semicrystalline structure is with the presence of mixed crys- (60:40) film the crystallinity increased to 24%. From these talline and amorphous phases.
Load more

Recommended publications
  • Study of MG49-PMMA Based Solid Polymer Electrolyte A
    170 The Open Materials Science Journal, 2011, 5, 170-177 Open Access Study of MG49-PMMA Based Solid Polymer Electrolyte A. Ahmad*,1,2, M.Y.A. Rahman*3, M.S. Su’ait1,2 and H. Hamzah1,2 1Polymer Research Center, Faculty of Sciences and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor, Malaysia 2School of Chemical Sciences and Food Technology, Faculty of Sciences and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor, Malaysia 3College of Engineering, Universiti Tenaga Nasional, 43009, Kajang, Selangor, Malaysia Abstract: The studies of rubber-polymer blends as solid polymer electrolyte for electrochemical devices application have been investigated. The electrolyte films were prepared by solution casting technique. The effect of poly(methyl methacrylate) (PMMA) and lithium tetrafluoroborate (LiBF4), salt concentration on chemical interaction, ionic conductivity, structure and morphology of 49% poly(methyl methacrylate)–grafted natural rubber (MG49) have been analyzed by using fourier transform infrared spectroscopy (FT-IR), electrochemical impedance spectroscopy (EIS), x-ray diffraction (XRD) and scanning electron microscopy (SEM). Infrared analysis showed that the interaction between oxygen atoms and lithium ion occurred at ether (C-O-C) and carbonyl (C=O) group in the MMA host. The highest ionic conductivity for blended MG49-PMMA films is 8.310-6 S cm-1 as compared to MG49 electrolyte with 9.610-10 S cm-1 at 25 wt. % LiBF4. The structural analysis showed the reduction of MMA crystallinity phase at the highest conductivity for both systems. Meanwhile, morphological analysis shows that recrystallization of LiBF4 salts have occurred in the electrolyte system after the optimum conductivity. Keywords: 49% poly(methyl methacrylate)–grafted natural rubber (MG49), ionic conductivity, lithium tetrafluoroborate (LiBF4), poly(methyl methacrylate) (PMMA), solid polymer electrolyte.
    [Show full text]
  • Electrolyte-Gated Organic Thin-Film Transistors
    Electrolyte-Gated Organic Thin-Film Transistors Lars Herlogsson Norrköping 2011 1 Electrolyte-Gated Organic Thin-Film Transistors Lars Herlogsson Linköping Studies in Science and Technology. Dissertations, No. 1389 Cover: Photographs of various transistors from the papers included in this thesis Copyright 2011 Lars Herlogsson, unless otherwise noted Printed by LiU-Tryck, Linköping, Sweden, 2011 ISBN 978-91-7393-088-8 ISSN 0345-7524 2 Abstract There has been a remarkable progress in the development of organic electronic materials since the discovery of conducting polymers more than three decades ago. Many of these materials can be processed from solution, in the form as inks. This allows for using traditional high-volume printing techniques for manufacturing of organic electronic devices on various flexible surfaces at low cost. Many of the envisioned applications will use printed batteries, organic solar cells or electromagnetic coupling for powering. This requires that the included devices are power efficient and can operate at low voltages. This thesis is focused on organic thin-film transistors that employ electrolytes as gate insulators. The high capacitance of the electrolyte layers allows the transistors to operate at very low voltages, at only 1 V. Polyanion-gated p- channel transistors and polycation-gated n-channel transistors are demonstrated. The mobile ions in the respective polyelectrolyte are attracted towards the gate electrode during transistor operation, while the polymer ions create a stable interface with the charged semiconductor channel. This suppresses electrochemical doping of the semiconductor bulk, which enables the transistors to fully operate in the field-effect mode. As a result, the transistors display relatively fast switching (! 100 "s).
    [Show full text]
  • 53187988.Pdf
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by ethesis@nitr PREPARATION AND CHARACTERIZATION OF POLYMER ELECTROLYTE Thesis submitted for the Award of degree of Master of Science by Suchetana Sadhukhan Under the Academic Autonomy National Institute of Technology, Rourkela Under the Guidance of Dr. Dillip Kumar Pradhan and Dr. Sidhartha Jena Department of Physics National Institute of Technology Rourkela-769008 1 | P a g e DECLARATION I hereby declare that the work carried out in this thesis is entirely original. It was carried out at Department of Physics, National Institute of Technology, Rourkela. I further declare that it has not formed the basis for the award of any degree, diploma, or similar title of any university or institution. Suchetana Sadhukhan Roll No- 409PH2104 Department of physics National Institute of Technology Rourkela-769008 2 | P a g e Department of Physics National Institute of Technology Rourkela – 769008 Odisha, India CERTIFICATE This is to certify that the thesis entitled “Preparation and Characterization of Polymer Electrolytes” being submitted by Suchetana Sadhukhan in partial fulfillment of the requirements for the award of the degree of Master of Science in Physics at National Institute of Technology, Rourkela is an authentic experimental work carried out by her under our supervision. To the best of our knowledge, the matter embodied in the thesis has not been submitted to any other University/Institute for the award of any degree or diploma. Date (Dr. Dillip Kumar Pradhan) (Dr. Sidhartha Jena) 3 | P a g e ACKNOWLEDGEMENT I humbly prostrate myself before the Almighty for his grace and abundant blessings which enabled me to complete this work successfully.
    [Show full text]
  • Preparation of Nanocomposite Polymer Electrolyte Via in Situ Synthesis of Sio2 Nanoparticles in PEO
    nanomaterials Article Preparation of Nanocomposite Polymer Electrolyte via In Situ Synthesis of SiO2 Nanoparticles in PEO Xinjie Tan 1, Yongmin Wu 2, Weiping Tang 2, Shufeng Song 1,*, Jianyao Yao 1, Zhaoyin Wen 3, Li Lu 4,5, Serguei V. Savilov 6,*, Ning Hu 7,8,* and Janina Molenda 9 1 College of Aerospace Engineering, Chongqing University, Chongqing 400044, China; [email protected] (X.T.); [email protected] (J.Y.) 2 State Key Laboratory of Space Power-sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China; [email protected] (Y.W.); [email protected] (W.T.) 3 CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; [email protected] 4 Department of Mechanical Engineering, National University of Singapore, Singapore 117575, Singapore; [email protected] 5 National University of Singapore Suzhou Research Institute, Suzhou 215000, China 6 Chemistry Department, M.V. Lomonosov Moscow State University, Moscow 119991, Russia 7 School of Mechanical Engineering, Hebei University of Technology, Tianjin 300401, China 8 State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing 400044, China 9 Faculty of Energy and Fuels, AGH University of Science and Technology, Al Mickiewicza 30, PL-30059 Krakow, Poland; [email protected] * Correspondence: [email protected] (S.S.); [email protected] (S.V.S.); [email protected] (N.H.) Received: 7 December 2019; Accepted: 13 January 2020; Published: 16 January 2020 Abstract: Composite polymer electrolytes provide an emerging solution for new battery development by replacing liquid electrolytes, which are commonly complexes of polyethylene oxide (PEO) with ceramic fillers.
    [Show full text]
  • Effect of Monomer Structure on Ionic Conductivity in a Systematic Set of Polyester Electrolytes
    Solid State Ionics 289 (2016) 118–124 Contents lists available at ScienceDirect Solid State Ionics journal homepage: www.elsevier.com/locate/ssi Effect of monomer structure on ionic conductivity in a systematic set of polyester electrolytes Danielle M. Pesko a, Yukyung Jung b, Alexandra L. Hasan a, Michael A. Webb c, Geoffrey W. Coates b, Thomas F. Miller III c,NitashP.Balsaraa,d,e,⁎ a Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA 94720, USA b Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA c Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA d Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA e Environmental Energy Technology Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA article info abstract Article history: Polymer electrolytes may enable the next generation of lithium ion batteries with improved energy density and Received 8 October 2015 safety. Predicting the performance of new ion-conducting polymers is difficult because ion transport depends on Received in revised form 23 February 2016 a variety of interconnected factors which are affected by monomer structure: interactions between the polymer Accepted 24 February 2016 chains and the salt, extent of dissociation of the salt, and dynamics in the vicinity of ions. In an attempt to unravel Available online 18 March 2016 these factors, we have conducted a systematic study of the dependence of monomer structure on ionic conduc- σ Keywords: tivity, , and glass transition temperature, Tg, using electrolytes composed of aliphatic polyesters and lithium fl Ionic conductivity bis(tri uoromethanesulfonyl) imide (LiTFSI) salt.
    [Show full text]
  • PEO Based Polymer-Ceramic Hybrid Solid Electrolytes: a Review
    Feng et al. Nano Convergence (2021) 8:2 https://doi.org/10.1186/s40580-020-00252-5 REVIEW Open Access PEO based polymer-ceramic hybrid solid electrolytes: a review Jingnan Feng1,2, Li Wang2, Yijun Chen1, Peiyu Wang1, Hanrui Zhang1 and Xiangming He2* Abstract Compared with traditional lead-acid batteries, nickel–cadmium batteries and nickel-hydrogen batteries, lithium- ion batteries (LIBs) are much more environmentally friendly and much higher energy density. Besides, LIBs own the characteristics of no memory efect, high charging and discharging rate, long cycle life and high energy conversion rate. Therefore, LIBs have been widely considered as the most promising power source for mobile devices. Commonly used LIBs contain carbonate based liquid electrolytes. Such electrolytes own high ionic conductivity and excellent wetting ability. However, the use of highly fammable and volatile organic solvents in them may lead to problems like leakage, thermo runaway and parasitic interface reactions, which limit their application. Solid polymer electrolytes (SPEs) can solve these problems, while they also bring new challenges such as poor interfacial contact with electrodes and low ionic conductivity at room temperature. Many approaches have been tried to solve these problems. This arti- cle is divided into three parts to introduce polyethylene oxide (PEO) based polymer-ceramic hybrid solid electrolyte, which is one of the most efcient way to improve the performance of SPEs. The frst part focuses on polymer-lithium salt (LiX) matrices, including their ionic conduction mechanism and impact factors for their ionic conductivity. In the second part, the infuence of both active and passive ceramic fllers on SPEs are reviewed.
    [Show full text]
  • Elastic Single-Ion Conducting Polymer Electrolytes: Towards A
    Elastic Single-ion Conducting Polymer Electrolytes: Towards a Versatile Approach for Intrinsically Stretchable Functional Polymers Peng-Fei Cao,* 1 Bingrui Li,2 Guang Yang,1 Sheng Zhao,2 Jacob Townsend,2 Kunyue Xing,2 Zhe Qiang,3 Konstantinos D. Vogiatzis,2 Alexei P. Sokolov,1,2 Jagjit Nanda,1 and Tomonori Saito*1 1 Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States 2 Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States 3 School of Polymer Science and Engineering, University of Southern Mississippi, Hattiesburg, Mississippi 39406, United States KEYWORDs: Functional polymer, Single-ion conducting, Elastic Polymer, Tunable mechanical properties Abstract: Fabrication of stretchable functional polymeric materials usually relies on the physical adhesion between functional components and elastic polymers, while the interfacial resistance is a potential problem. Herein, a versatile approach on the molecular-level intrinsically stretchable polymer materials with defined functionality is reported. The single-ion conducting polymer electrolytes (SICPEs) were employed to demonstrate the proposed concept along with its potential application in stretchable batteries/electronics with improved energy efficiency and prolonged cell lifetime. The obtained membranes exhibit 88-252% elongation before break, and the mechanical properties are well adjustable. Galvanostatic test of the assembled cells using the obtained SICPE membrane exhibited good cycling performance with
    [Show full text]
  • Transparent Ionic Liquid-Phenol Resin Hybrids with High Ionic Conductivity
    Polymer Journal (2011) 43, 421–424 & The Society of Polymer Science, Japan (SPSJ) All rights reserved 0032-3896/11 $32.00 www.nature.com/pj ORIGINAL ARTICLE Transparent ionic liquid-phenol resin hybrids with high ionic conductivity Tomoki Ogoshi1, Takeshi Onodera1, Tada-aki Yamagishi1, Yoshiaki Nakamoto1, Akihito Kagata2, Noriyoshi Matsumi2 and Keigo Aoi2 We report transparent ion conductive ionic liquid-phenol resin hybrids prepared by in situ polymerization/crosslinking of phenol monomer in ionic liquid. As ionic liquid, we used highly ion conductive ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([EMI][TFSA]). Simultaneous polymerization and crosslinking of phenol with paraformaldehyde in [EMI][TFSA] yielded a highly transparent film. From a field emission scanning electron microscope (FE-SEM) image at 5000 magnification, the transparent hybrid prepared by in situ method did not show phase separation at 5000 magnification. In addition, from the FE-SEM image of the transparent hybrid at high magnification (Â60 000), phenol resin and [EMI][TFSA] were observed to be integrated at a scale of a few nanometers. The transparent hybrid containing 20 wt% phenol resin showed high thermal stability and ionic conductivity (1.0Â10À3 ScmÀ1 at 30 1C), which is comparable to the pristine ionic liquid [EMI][TFSA]. Polymer Journal (2011) 43, 421–424; doi:10.1038/pj.2011.1; published online 16 February 2011 Keywords: hybrid materials; ionic conductivity; ionic liquids; phenol resin; solid polymer electrolyte INTRODUCTION By using
    [Show full text]
  • Solid Polymer Electrolytes Derived from Crosslinked Polystyrene Nanoparticles Covalently Functionalized with a Low Lattice Energy Lithium Salt Moiety
    chemengineering Article Solid Polymer Electrolytes Derived from Crosslinked Polystyrene Nanoparticles Covalently Functionalized with a Low Lattice Energy Lithium Salt Moiety Xinyi Mei 1, Wendy Zhao 1, Qiang Ma 1, Zheng Yue 1, Hamza Dunya 1 , Qianran He 2, Amartya Chakrabarti 3, Christopher McGarry 1 and Braja K. Mandal 1,* 1 Department of Chemistry, Illinois Institute of Technology, Chicago, IL 60616, USA; [email protected] (X.M.); [email protected] (W.Z.); [email protected] (Q.M.); [email protected] (Z.Y.); [email protected] (H.D.); [email protected] (C.M.) 2 Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago, IL 60616, USA; [email protected] 3 Department of Physical Sciences, Dominican University, River Forest, IL 60305, USA; [email protected] * Correspondence: [email protected] Received: 3 May 2020; Accepted: 6 July 2020; Published: 16 July 2020 Abstract: Three new crosslinked polystyrene nanoparticles covalently attached with low lattice energy lithium salt moieties were synthesized: poly(styrene lithium trifluoromethane sulphonyl imide) (PSTFSILi), poly(styrene lithium benzene sulphonyl imide) (PSPhSILi), and poly(styrene lithium sulfonyl-1,3-dithiane-1,1,3,3-tetraoxide) (PSDTTOLi). A series of solid polymer electrolytes (SPEs) were formulated by mixing these lithium salts with high molecular weight poly(ethylene oxide), poly(ethylene glycol dimethyl ether), and lithium bis(fluorosulfonyl)imide. The crosslinked nano-sized polymer salts improved film strength and decreased the glass transition temperature (Tg) of the polymer electrolyte membranes. An enhancement in both ionic conductivity and thermal stability was observed. For example, the SPE film containing PSTFSILi displayed ionic conductivity of 7.52 10 5 S cm 1 at room temperature and 3.0 10 3 S cm 1 at 70 C, while the SPE film containing × − − × − − ◦ PSDTTOLi showed an even better performance of 1.54 10 4 S cm 1 at room temperature and × − − 3.23 10 3 S cm 1 at 70 C.
    [Show full text]
  • Ion Diffusion and Electrochemically Driven Transport in Homogenous and Nanostructured Polymer Electrolytes
    Ion Diffusion and Electrochemically Driven Transport in Homogenous and Nanostructured Polymer Electrolytes By Ksenia Timachova A dissertation submitted for the degree of Doctor of Philosophy in Chemical Engineering in the Graduate Division of the University of California, Berkeley Committee Members Professor Nitash P. Balsara, Chair Professor Bryan D. McCloskey Professor Phillip Messersmith Summer 2018 © Copyright 2018 Ksenia Timachova All rights reserved. Abstract Ion Diffusion and Electrochemically Driven Transport in Homogenous and Nanostructured Polymer Electrolytes by Ksenia Timachova Doctor of Philosophy in Chemical Engineering University of California, Berkeley Professor Nitash P. Balsara, Chair There is a growing need for safe, reliable, economical, and energy dense electrical energy storage devices. Polymer electrolytes are of great interest due to their potential use in high specific energy solid-state batteries. Polymer electrolytes are mixtures containing dissociated ions in a polymer matrix. The transport of ions in polymer electrolytes is of significant practical interest in order to enable their use and commercialization in next generation energy storage devices. Most experimental work on the field has focused on studying bulk electrochemical transport properties such as ionic conductivity. In this work, ion transport is primarily studied using a spectroscopic technique called pulsed-field gradient NMR (PFG-NMR). Using this technique, we investigate the molecular mechanisms that dictate ion transport through polymer materials. Polyethylene oxide (PEO) provides a useful model system to study the effects of molecular weight and salt concentration on ion transport. We present measurements of the electrochemical transport properties of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in PEO over a wide range of PEO molecular weights and salt concentrations.
    [Show full text]
  • Preparation and Proton Conductivity of Polymer Electrolytes Based on Alginic Acid and 1,2,4-Triazole
    #2008 The Society of Polymer Science, Japan Preparation and Proton Conductivity of Polymer Electrolytes Based on Alginic Acid and 1,2,4-Triazole By Seyda T. GU¨ NDAY and Ayhan BOZKURTÃ In this work, novel proton conducting anhydrous polymer electrolytes based on alginic acid (AL) and 1,2,4-Triazole (Tri) were investigated. The biomaterials were prepared by the combination of alginic acid with a heterocyclic protogenic solvent, 1,2,4-triazole at several molar ratios, x to form ALTrix. The materials can be cast into transparent, homogeneous thin films (50–100 mm). FT-IR spectroscopy suggested the proton exchange reactions between –COOH group of AL and Tri. Thermal properties of the materials were studied via thermogravimetic analysis (TG) and differential scanning calorimetry (DSC). The X-ray diffraction (XRD) study reveals the amorphous nature of the ALTrix electrolytes. Proton conductivity increases with the Tri content and ALTri1:5 exhibited approximate maximum conductivity of 0:1 mS/cm at 100 C. KEY WORDS: Alginic Acid / Triazole / Biomaterials / Polymer Electrolyte / Proton Conductivity / Alginic acid is a naturally occurring biopolymer obtained three nitrogen atoms in the ring. The use of 1,2,4-triazole (Tri) from the various species of brown seaweed. It is a linear as proton transport facilitator in acidic biopolymers can be a copolymer consisting of (1-4)-linked -D-mannuronate (M) new avenue for the development of non-aqueous polymer and -L-guluronic acid (G) which are covalently linked electrolytes. The molecular structure of Tri
    [Show full text]
  • Nanosponge-Based Composite Gel Polymer Electrolyte for Safer Li-O2 Batteries
    polymers Article Nanosponge-Based Composite Gel Polymer Electrolyte for Safer Li-O2 Batteries Julia Amici 1,* , Claudia Torchio 1, Daniele Versaci 1, Davide Dessantis 1, Andrea Marchisio 1, Fabrizio Caldera 2 , Federico Bella 1 , Carlotta Francia 1 and Silvia Bodoardo 1 1 Electrochemistry Group, Department of Applied Science and Technology, Politecnico di Torino, C.so D.ca degli Abruzzi 24, 10128 Torino, Italy; [email protected] (C.T.); [email protected] (D.V.); [email protected] (D.D.); [email protected] (A.M.); [email protected] (F.B.); [email protected] (C.F.); [email protected] (S.B.) 2 Department of Chemistry, Università degli Studi di Torino, Via Pietro Giuria 7, 10125 Torino, Italy; [email protected] * Correspondence: [email protected] Abstract: Li-O2 batteries represent a promising rechargeable battery candidate to answer the energy challenges our world is facing, thanks to their ultrahigh theoretical energy density. However, the poor cycling stability of the Li-O2 system and, overall, important safety issues due to the formation of Li dendrites, combined with the use of organic liquid electrolytes and O2 cross-over, inhibit their practical applications. As a solution to these various issues, we propose a composite gel polymer electrolyte consisting of a highly cross-linked polymer matrix, containing a dextrin-based nanosponge and activated with a liquid electrolyte. The polymer matrix, easily obtained by thermally activated Citation: Amici, J.; Torchio, C.; one pot free radical polymerization in bulk, allows to limit dendrite nucleation and growth thanks to Versaci, D.; Dessantis, D.; Marchisio, its cross-linked structure.
    [Show full text]