F. Svegl et al., SPECTROELECTROCHEMICAL AND STRUCTURAL-PROPERTIES OF ELECTROCHROMIC CO(AL)-OXIDE AND CO(AL,SI)-OXIDE FILMS PREPARED BY THE SOL-GEL ROUTE, Journal of electroanalytical chemistry [1992], 418(1-2), 1996, pp. 53-66
New electrochromic spinel-type Co(Al)-oxide and Co(Al,Si)-oxide films
exhibiting coloring/bleaching changes Delta T=T-colored-T-bleached =75
%-25%=50% (where T is transmittance) with a coloring efficiency of 22c
m(2) C-1 were deposited by a dip-coating method from aqueous colloidal
solutions made by thermal hydrolysis of Co(II)-acetate, Al(III)-sulph
ate, citric acid and 3-aminopropyltriethoxysilane precursors. The nano
composite spinel structure of the films and powders was determined usi
ng X-ray diffraction, thermogravimetry, visible and infrared transmiss
ion and reflection-absorption spectroscopy performed at near-grazing i
ncidence angle conditions (80 degrees) using p-polarized light The exi
stence of spinel lattice modes in the IR spectra of cycled films prove
d that the spinel structure of Co(Al,Si)-oxide films is preserved at l
east on the scale of short-range interactions detected with IR spectro
scopy, In addition to this, sulphate (SO42-) ions are retained in the
structure of cycled films heat-treated at 500 degrees C. The role of o
rder-disorder transitions of sulphate ions present in cycled films is
discussed with respect to their influence in enhancing the speed and d
egree of coloring/bleaching changes of electrochromic Co(Al,Si)-oxide
spinel films.