Characterization of solid polymer electrolytes based on poly(trimethylenecarbonate) and lithium tetrafluoroborate (original) (raw)
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2015
Solid polymer electrolytes composed of poly (vinylidene fluoridecohexafluoro propylene) (PVdFHFP) and various concentrations of lithium trifluoromethanesulfonate (lithium triflate) were prepared by the solution casting technique in order to determine the optimal composition of the lithium salt for maximum ionic conductivity. Structural changes and complex formations of the polymersalt systems were ascertained from xray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy studies. Scanning electron microscope (SEM) investigation results confirm morphological changes upon the addition of the salt to the polymer. Measurements of the temperaturedependent ionic conductivity of the electrolytes were performed in the temperature range 303 � 393 K using a DC conductivity setup. The results reveal that the ionic conductivity of the polymer electrolytes containing various salt concentrations increases with temperature and obeys the Arrhenius rule. Also, it was found that the e...
Solid State Ionics, 2018
Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3) 2 , LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO 2 F) 2 , LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36 × 10 −4 S/cm at 80°C and 1.01 × 10 −5 S/cm at 20°C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25 × 10 −3 S/cm at 80°C and 5.93 × 10 −5 S/cm at 20°C. Glass transition temperature (T g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.
Polymer electrolytes based on polycarbonates and their electrochemical and thermal properties
Ionics, 2012
Polycarbonates (4a-d) with various side chain lengths were synthesized by the reaction of 1,4-bis(hydroxyethoxy)benzene derivatives and triphosgene in the presence of pyridine. The polymer electrolytes composed of 4a-d with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3) 2 , LiTFSI) were prepared, and their ionic conductivities and thermal and electrochemical properties were investigated. 4d-Based polymer electrolyte showed the highest ionic conductivity values of 1.0×10 −4 S/cm at 80°C and 1.5×10 −6 S/cm at 30°C, respectively, at the [LiTFSI]/[repeating unit] ratio of 1/2. Ionic conductivities of these polycarbonate-based polymer electrolytes showed the tendency of increase with increasing the chain length of oxyethylene moieties as side chains, suggestive of increased steric hindrance by side chains. Unique properties were observed for the 4a(n00)-based polymer electrolyte without an oxyethylene moiety. All of polycarbonate-based polymer electrolytes showed good electrochemical and thermal stabilities as polymer electrolytes for battery application.
Thermal and electrochemical properties of poly(butylene sulfite)-based polymer electrolyte
Ionics, 2017
Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3) 2 , LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO 2 F) 2 , LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36 × 10 −4 S/cm at 80°C and 1.01 × 10 −5 S/cm at 20°C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25 × 10 −3 S/cm at 80°C and 5.93 × 10 −5 S/cm at 20°C. Glass transition temperature (T g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.
Solid polymer electrolytes composed of polyanionic lithium salts and polyethers
Journal of Power Sources, 2009
Solid polymer electrolytes are prepared by the combination of a polyether, poly(ethylene oxide) (PEO) or poly(ethylene oxide-co-propylene oxide) (P(EO/PO)), and a polyanionic lithium salt, (poly(lithium sorbate) (Poly(Li-Sorb)) or poly(lithium muconate) (Poly(Li-Muco)), and their ionic conductivities, lithium ion transference number, electrochemical stabilities, thermal properties, and mechanical strength were investigated in the absence and presence of BF 3 •OEt 2. The ionic conductivities of all solid polymer electrolytes were enhanced by one to two orders of magnitude with addition of BF 3 •OEt 2 , because the dissociation of lithium ion and carboxylate anion was promoted by complexation with BF 3. The lithium ion transference number in these solid polymer electrolytes showed relatively high values of 0.45-0.88, due to the suppression of the transport of the large counter polymeric anion. These solid polymer electrolytes showed good electrochemical and thermal stabilities, and also, the mechanical strength of the solid polymer electrolytes was improved by the function of crystalline poly(lithium carboxylate)s as a sort of filler.
All-solid batteries using polymer electrolytes have been accepted as a final target of lithium secondary batteries. This is because the polymer electrolytes in place of conventionally used organic electrolyte solutions are expected to demonstrate high safety performance against an accident such as thermal shock during utilization. Furthermore, the final system of all-solid batteries could be simplified without a sealed package, separator between electrodes, and any additional apparatus to assure safety. This advantage could contribute to the cost reduction of battery bodies and of the fabrication process.
Characteristics of a poly (ethylene oxide)-LiBF4 polymer electrolyte
The poly(ethylene oxide)-lithium tetrafluoborate complex, (PEO)7LiBF 4, has been characterized in terms of total and electronic conductivity, lithium transport number, stability versus lithium electrode and thermal properties. The results indicate that this polymeric electrolyte offers promises of application in lithium-based electrochemical devices.
Ionics, 2007
Gel polymer polymer membranes, prepared by immobilizing lithium-conducting solutions in a polymer matrix, are promising electrolyte materials for promoting the advancement of the lithium battery technology. However, so far, not much attention has been devoted to the definition of the role of the constituents in determining the properties of these electrolytes. In this work we have examined the characteristics of three common examples of polymer electrolytes based on a poly(vinylidene fluoride)-fluoropropylene, poly(vinyilidene fluoride)–hexa-fluoropropylene copolymer matrix. The three selected electrolytes differed from the nature of their polymer matrix. The results, based on X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and conductivity tests, show that, indeed, the type of the polymer matrix may influence the properties of the electrolytes, especially in terms of conductivity.
Electrical and electrochemical studies on sodium ion-based gel polymer electrolytes
AIP Conference Proceedings, 2017
Gel polymer electrolytes (GPEs) have captured great attention because of their unique properties such as good mechanical stability, high flexibility and high conductivity approachable to that of the liquid electrolytes. In this work, we have prepared sodium ion conducting gel polymer electrolyte (GPE) films consisting of polyvinylidenefluoride-cohexafluoropropylene (PVdF-HFP) as a polymer host using the solution casting technique. Sodium trifluoromethanesulfonate (NaCF 3 SO 3) was used as an ionic salt and the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizing solvent. Impedance spectroscopy measurements were carried out to determine the ionic conductivity of the GPE films. The sample containing 20 wt.% of NaCF 3 SO 3 salt exhibits the highest room temperature ionic conductivity of 2.50 x 10-3 S cm-1. The conductivity of the GPE films was found to depend on the salt concentration that added to the films. The ionic and cationic transference numbers of GPE films were estimated by DC polarization and the combination of AC and DC polarization method, respectively. The results had shown that both ionic and cationic transference numbers are consistent with the conductivity studies. The electrochemical stability of the GPE films was tested using linear sweep voltammetry (LSV) and the value of working voltage range appears to be high enough to be used as an electrolyte in sodium batteries. The cyclic voltammetry (CV) studies confirmed the sodium ion conduction in the GPE films.
2011
The effect of different plasticizers on the properties of PAN-LiCF(3)SO(3) polymer electrolytes has been studied. Propylene carbonate (Pc) and ethylene carbonate (EC) having different values of donor numbers, dielectric constant and viscosity have been used as plasticizers. The highest room temperature conductivity for the film in the PAN-LiCF(3)SO(3) system was 3.04 x 10(-4) s cm(-1). The highest room temperature conductivity for the films in the PAN-EC-LiCF(3)SO(3) system and the PAN-PC-LiCF(3)SO(3) system was 1.32 x 10(-3) and 8.64 x 10(-4) S cm(-1). The addition of plasticizers has been found to enhance the conductivity of polymer electrolytes by increasing the amorphous content as well as by dissociating the ion aggregates present in polymer electrolyte. Conductivity temperature-dependence studies of these plasticized PAN-salt systems were carried out in the temperature range of 303 to 373 K. The conductivity versus temperature plots obeyed an Arrhenius type variation. The structural and complex formations were studied by X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy.