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Electron transport and frozen concentration gradients in a mixed valent viologen molten salt

Journal Article · · Journal of Physical Chemistry
; ;  [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States)

This paper shows that electrolytically generated crossed concentration gradients of viologen (2+) and viologen (1+) in films of its mixed valent molten salt on interdigitated array electrodes can be thermally and stably frozen in place in the interelectrode gaps. A study is presented of properties of the gradient-containing films, as compared to films that are non-mixed valent (V{sup 2+}) or that are mixed valent but lack concentration gradients. Comparisons of charge transport measurements show that the 2-5 {mu}m wide concentration gradients are persistent in the molten salt at lowered temperatures, where ionic motions are quenched relative to electron hopping as shown by differences in conductivity between mixed valent and non-mixed valent films as the temperature is lowered from +50 to -70{degree}C. Differences in the magnitude and shape of high-field current-voltage curves taken from mixed valent nongradient and V{sup 2+}/V{sup +} gradient-containing samples are interpreted with an electron-hopping model that includes a parameter for kinetic dispersity. Differences between the capacitance of the mixed valent and non-mixed valent phase of the viologen molten salt are consistent with the formation of an electronic space charge at the metal/redox conductor interface. 18 refs., 8 figs., 1 tab.

Sponsoring Organization:
USDOE
OSTI ID:
171502
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 45 Vol. 99; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English

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