Design and synthesis of new anionic “polymeric ionic liquids” with high charge delocalization

Abstract

Three novel ionic monomers having highly delocalized anions and electrochemically stable mobile cations, namely, 1-butyl-1-methylpyrrolidiniumpropylsulfonyl)]methanide and 1-butyl-1-methylpyrrolidinium 1-cyano-1- [(3-(methacryloyloxy) propylsulfonyl)]imide were synthesized and characterized. The structure of these monomers was designed to be a mimic of the most highly conductive bis(trifluoromethylsulfonyl)imide, tricyanomethanide and dicyanamide anions. By radical polymerization procedure a series of new anionic ''polymeric ionic liquids'' (PILs) were prepared. The solubility of these linear PILs, thermal stability, glass transition temperatures, molar masses and ionic conductivities were estimated. An advantage of the novel PILs was demonstrated by the comparison of their ionic conductivity at 25 C (2.0 Â 10 À8 O 1.6 Â 10 À7 S cm À1 ) with the unmodified poly(1-ethyl-1-methylpyrrolidinium 3-(methacryloyloxy)propane-1-sulfonate) analog. The increase in ionic conductivity is as high as three orders of magnitude and was found to depend on the size of the attached anion. The new ionic monomers were subsequently copolymerized with poly(ethylene glycol) dimethacrylate and poly (ethylene glycol) methyl ether methacrylate. The investigation of the copolymers properties revealed further improvement of the conductivity in approximately two orders of magnitude and the achievement of s ¼ 4.8 O 6.8 Â 10 À6 S cm À1 ) at 40 C.

Solid polymer electrolyte comprised of lithium salt/ether functionalized ammonium-based polymeric ionic liquid with bis(fluorosulfonyl)imide

“…The bis(fluorosulfonyl)imide ([N(SO 2 F) 2 ] − , FSI − ) anion is a homologue of TFSI − anion, and in recent years both lithium salt (i.e., lithium bis(fluorosulfonyl)imide, LiFSI) and ionic liquids (ILs) with FSI − anion have been intensively studied as electrolyte materials for Li and Li-ion battery [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38], because of its excellent compatibility with various electrodes, such as Li metal [25,29], graphitized carbon [26][27][28], and silicon [33] anodes and LiFePO 4 and LiCoO 2 cathodes in conventional liquid carbonate electrolyte [31,32], room temperature ionic liquids [25][26][27][28][29], ambient temperature molten salt [30,34,35], and polymer electrolyte systems [23,24,36,37]. Additionally, FSI − anion displays better plasticizing effect than TFSI − anion, which could significantly reduce the glass transition temperature (T g ) and increase the ionic conductivities of polymer electrolytes (e.g., lower T g and higher conductivities for both…”

“…Currently, there is a growing interest in the design and preparation of polymeric ionic liquids (PILs) as safe electrolytes for the application in electrochemical devices, such as Li and Li-ion battery [1][2][3][4][5][6][7], solar-cells [8,9], fuel cells [10][11][12] and supercapacitors [13,14]. This is mainly motivated by the combination of both the advanced properties of conventional ionic liquids (ILs) and the flexibility and mechanical properties of polymers [15][16][17].…”

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

“…LiAPTFSI was synthesized via a previously reported procedure [56]. Briefly, the purchased potassium 3-(acryloyloxy)propane-1-sulfonate was dried and then converted to 3-(chlorosulfonyl)propyl acrylate via reaction with excess thionyl chloride.…”

Supramolecular ionic networks with superior thermal and transport properties based on novel delocalized di-anionic compounds

“…The choice of the latter was driven by the desire to reduce the asymmetry and subsequent melting point of the final ionic monomers. The two steps synthetic route of 3, 4, 7 and 8 was similar to the procedure published by some of us 15 previously 19 in the case of methacrylic anionic monomers. On the first stage 1,4-butanedisulfonic acid disodium salt or benzene-1,3-disulfonic acid disodium salt were converted into their respective sulfonyl chloride derivatives by reaction with thionyl chloride in the presence of DMF as a catalyst.…”