7Li NMR, ionic conductivity and self-diffusion coefficients of lithium ion and solvent of plasticized organic–inorganic hybrid electrolyte based on PPG-PEG-PPG diamine and alkoxysilanes

• Published in: Electrochimica acta 2006-11, Vol.52 (3), p.1015-1027
• Main Authors: Kao, Hsien-Ming, Chang, Pai-Ching, Chao, Shih-Wei, Lee, Chiou-Hwang
• Format: Article
• Language: English
• Subjects: Chemistry; Diffusion coefficients; Electrochemistry; Exact sciences and technology; General and physical chemistry; Ionic conductivity; Organic–inorganic hybrid; Plasticizer; Properties of electrolytes: conductivity; Solid-state NMR
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2006.06.042

Organic–inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO 4 via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10 −3 S/cm at 30 °C. Variable temperature 7Li–{ 1H} magic angle spinning (MAS) NMR demonstrated that the Li + cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the 7Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.