Blends of Poly(meth)acrylates with 2-Oxo-(1,3)dioxolane Side Chains and Lithium Salts as Lithium Ion Conductors

Abstract

A novel approach is described to obtain polymers which show significant lithium ion conductivity when blended with lithium salts. Polymerization of acrylates and methacrylates with 2-oxo-1,3-dioxolane (cyclic carbonate) containing side chains gives polymers which contain the structural element of the prototypical solvent propylene carbonate (PC) firmly attached to the polymer host. (2-Oxo-1,3-dioxolane-4-yl)methyl methacrylate (DOMA) and the corresponding acrylate (DOA) were obtained by reaction of the (meth)acryloyl chloride with glycerol carbonate while (2-oxo-1,3-dioxolane-4-yl)butyl methacrylate (DOBMA) and the respective acrylate (DOBA) were obtained from the ω-hexenyl esters by first epoxidation followed by CO 2 -insertion into the oxirane ring. Free radical polymerization in DMF gave the desired polymers. All homopolymers were thermally stable at least up to 200 °C; the glass transition temperature was found for PDOMA at 93 °C, for PDOA at 50 °C, for PDOBMA at 16 °C, and for PDOBA at 11 °C. Free radical copolymerization of DOMA with butyl methacrylate (BMA) (r 1 ) 1.24, r 2 ) 0.80) gave copolymers with T g dependent on the BMA content. Blends of the homopolymers with lithium bis(trifluoro)methane sulfonimide (LiTFSI) gave appreciable lithium ion conductivities, particularly for blends of PDOA (3.7 × 10 -6 S cm -1 at 40 °C) which could be substantially increased by further blending with small amounts of propylene carbonate. These blends of honey-like consistency showed conductivities of 1.8 × 10 -3 S cm -1 (40 °C) for PDOA and 5.1 × 10 -4 S cm -1 (40 °C) for PDOBMA each blended with LiTFSI and PC at equimolar amounts. The temperature dependence of lithium ion conductivity follows a WLFtype behavior in all cases; however, the reference temperatures do not bear any correspondence to the observed glass transition temperatures but are estimated from modified WLF-plots to be positioned in a temperature regime typical for local side chain relaxations in common polymers.

Conductivity Study on PEO Based Polymer Electrolytes Containing Hexafluorophosphate Anion: Effect of Plasticizer

“…Philips analytic X-ray diffractometer (with copper as a source of K a radiation having wavelength 1.5415A8) has been used to study XRD patterns of different polymer electrolytes. 1 H NMR spectra at different temperatures were measured by using home made pulsed spectrometer at 6.4 T with a corresponding Larmor frequency of 271.3 MHz. Surface morphology of different polymer electrolytes has been studied by Hitachi S-4700 scanning electron microscope at an accelerating voltage of 10 KV.…”

“…[1][2][3] Among the different solid polymer electrolytes, proton conducting polymer electrolytes have also attracted attention due to their possible use in fuel cells, electrochromic devices, sensors etc. [4][5][6] The essential requirements of the materials for such applications are high ambient ionic conductivity, high thermal and mechanical stability.…”

Systematical, experimental investigations on LiMgZ (Z = P, As, Sb) wide band gap semiconductors

“…IS was recorded as a function of temperature from -120 • C to 180 • C [Solartrin SI 1260 impedance gain phase analyzer with a high-resolution dielectric converter-Alpha high-resolution dielectric analyzer Novocontrol [15] in the range from 10 −1 -10 6 Hz]. The measurements were performed using stainless steel or platinum electrodes with 10 or 20 mm diameter under nitrogen flow.…”

Synthesis of Glyceryl Carbonate via Microwave Irradiation

“…Gly-C was proposed as a promising biobased alternative in both direct and indirect applications. It was described to have potential application as a solvent in various applications (Kreutzberger, 2000;Schaffner et al, 2010), in development of rechargeable lithium batteries (Baril et al, 1997;Britz et al, 2007), a part of membrane component for gas separation (Kovvali and Sirkar, 2002), as a component of surfactants and detergents (Ghandi et al, 2007;Iaych et al, 2011) and as monomer of polycarbonate and polyurethane (Kob et al, 2007).…”