Synthesis and Characterization of Ionically Conducting Alkoxy Ether/Alkoxy Mixed-Substituent Poly(organophosphazenes) and Their Use as Solid Solvents for Ionic Conduction

Abstract

A series of mixed-substituent poly(organophosphazenes) with the general structure {NP[OCH2CH2OCH2CH2OCH3] x [O(CH2) y CH3]2-x } n , where x = 1 and y = 2−9 was synthesized. These polymers are candidates for use as solid polymeric, ionic conduction media. The polymers were characterized by 1H, 13C, and 31P nuclear magnetic resonance spectroscopy, gel permeation chromatography, elemental microanalysis, infrared spectroscopy, and differential scanning calorimetry. The polymers were complexed with LiSO3CF3 and ambient temperature (25 °C) ionic conductivity studies were performed with the use of complex impedance analysis. The effect of changes in the length of the alkyl component of the alkoxy groups on conductivity was examined. A maximum conductivity as a function of the concentration of lithium triflate was found for each system. The conductivity decreased with an increase in the alkyl group side-chain length. These polymers were compared to the polyphosphazene single-substituent polymer [NP(OCH2CH2OCH2CH2OCH3)2] n , as well as to the n-alkyloxy single-substituent polymers {NP[O(CH2) x CH3]2} n , where x = 2−9.

Transport Mechanisms of Ions in Graft-Copolymer Based Salt-in-Polymer Electrolytes

“…Detailed characterizations were carried out by methods like infrared spectroscopy [29][30][31], nuclear magnetic resonance (NMR) [32][33][34][35][36][37][38][39][40] and viscosimetry [41][42][43][44] in order to clarify the interaction of the cations with a polymer network and their associated transport dynamics.…”

Synthesis and ionic conductivity of mixed substituted polysiloxanes with oligoethyleneoxy and cyclic carbonate substituents

“…However, PEOLiX complexes exhibit very low ambient conductivity, typically 10 −7 S/cm. Recently, several classes of polymer electrolytes based on comb polyphosphazene [17][18][19][20][21][22][23][24][25], polysiloxane [26][27][28][29][30][31][32][33][34][35] and borane containing polyethers [36] were found to exhibit higher ambient ionic conductivity. These results demonstrated that apWe dedicate this paper to Professor Dick Jones, polysilane pioneer and valued friend.…”

Silicon-Containing Carbonates—Synthesis, Characterization, and Additive Effects for Silicon-Based Polymer Electrolytes

“…Over the past three decades, ion-conducting polymers have been investigated as promising and safe alternatives to the commercially available electrolytes currently used in lithium batteries [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. The initial discoveries that polymer complexes could be used as either liquid [1] or solid [2] ionic conductors has led to the development of a wide range of polymer-based electrolytes.…”

“…However, PEO is crystalline at room temperature and can be electrochemically unstable. Therefore, efforts have focused on the combination of PEO with amorphous polymers such as polyphosphazenes [3][4][5][6][7][8] and polysiloxanes [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] via copolymerization reactions.…”

“…Although significant research has concentrated on the development of polysiloxane-PEO copolymer structures, alternative polymer electrolytes structures have also been investigated [3][4][5][6][7][8][27][28][29]. For example, Wnek and coworkers [27] introduced carbonate groups onto the polysiloxane backbone in order to study them as potential polymer electrolytes.…”