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Title: Synthesis, physical and electrical characterization of polymer electrolytes and polymer complexes containing polyhalides

Miscellaneous ·
OSTI ID:7267787

The conductivity and dielectric response was determined for poly (propylene oxide) (PPO), the polymeric solid electrolytes (PPO)[sub 8]NH[sub 4]SO[sub 3]CF[sub 3], (PPO)[sub 16]NaI, (PPO)[sub 10]NaI and (PPO)[sub 8]NaI and the sodium polyiodide complex, (PPO)[sub 8]NaI[sub 9], in the frequency range from dc to 6 GHz and the temperature range from 173-323 K at 3 GHz. These data were used to make the first comparisons between an amorphous host polymer and its salt complexes. The addition of salt to PPO results in a considerable change in dielectric properties. The dielectric loss spectrum of PPO displays a broad [beta]-relaxation attributed to the micro-Brownian motion of the polymer while no appreciable relaxation peak is observed for (PPO)[sub 8]NH[sub 4]SO[sub 3]CF[sub 3]. The conductivity of the previously characterized (PEO)[sub 8]NH[sub 4]SO[sub 3]CF[sub 3] is higher than (PPO)[sub 8]NH[sub 4]SO[sub 3]CF[sub 3] over the entire frequency range covered. The methyl group on PPO apparently sterically restricts the local motions of the polymer necessary for ion conduction. The dielectric loss spectrum of (PPO)[sub 8]NaI displays a narrow relaxation peak around 10 MHz, possibly associated with the motions of NaI aggregates. (PPO)[sub 8]NaI[sub 9] displays a much higher conductivity than simple polymer-salt complexes. The lack of frequency dependence of the (PPO)[sub 8]NaI[sub 9] conductivity compared to that of the simple polymer-salt complexes suggests that long range charge transport in (PPO)[sub 8]NaI[sub 9] is dominated by a process that is much faster than the diffusion of ions in the polymer solvent. Resonance Raman spectra reveal the presence of a rich variety of polyhalide species in the products resulting from the addition of Br[sub 2], IBr or I[sub 2] to PPO-LiBr or PPO-LiI salt complexes. Impedance measurements demonstrate high bulk conductivities. There appears to be little correlation between conductivity and iodine or bromine content.

Research Organization:
Northwestern Univ., Chicago, IL (United States)
OSTI ID:
7267787
Resource Relation:
Other Information: Thesis (Ph.D.)
Country of Publication:
United States
Language:
English