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As noted above, many other thin-film metal oxides (13), for example, the
oxides of molybdenum and vanadium (13), are electrochromic:
MoO3 colorless + x(M+ + e) = HxMoVI (1x) MoV x O3 deep blue
V2O5 brown-yellow + x(M+ + e) = MxVIV (1x) VV x O5 very pale blue .
In his device, electrochromic coloration occurred on application of 104 V cm1
across a thin film of highly disordered, vacuum-deposited WO3 on quartz.
In these examples, the more intensely absorbing redox state is produced on
reduction, with concurrent cation insertion. In contrast, group VIII metal oxides
become colored on electrochemical oxidation, as in the case of hydrated
iridium oxide (iridium hydroxide). The mechanism of coloration is uncertain;
both proton extraction and anion insertion routes are proposed:
Ir(OH)3 colorless = IrO2 H2O + H+ + e blue-gray ,
Ir(OH)3 + OH colorless = IrO2 H2O + H2O + e blue-black .
Ni(OH)2 pale green + OH = NiO OH brown-black + H2O + e.
Preparation of Thin-Film Metal Oxides For ECD application,
metal oxides must be deposited on a conducting substrate as a thin, even film,
typically in the range of 0.20.5 m. Such thin films are either amorphous or
polycrystalline, sometimes both admixed, and the morphology depends
strongly on the mode of film preparation. Granqvists book (3) and reviews give
extensive detail on the preparation of metal oxide films. Deposition methods
have been outlined (1) and comprise chemical vapor deposition,
electrodeposition, sol-gel techniques (spray pyrolysis, dip and spin coating),
sputtering in vacuo (using dc magnetron, electron beam, and radio frequency
radiation), thermal deposition in vacuo, and Langmuir-Blodgett deposition.
This type of ECD therefore requires passage of a continuous small current for
replenishment of the colored electroactive species lost by their mutual selferasing solution redox reaction. A solution-phase electrochromic system in
acetonitrile comprising nine solution-phase electrochromic thin-layer cells
based on HV perchlorate and N,N ,N,N -tetramethyl-1,4-phenylenediamine
(TMPD) has been investigated for display applications (43). Equation 9 shows
the spontaneous reaction between the radical cations that is associated with
bleaching, whereas the electrolytic reverse reaction generates an intense blue
coloration:
The influences of operating voltage and cell gap have been investigated in a
solution-phase ECD containing HV and TMPD in propylene carbonate, with 0.5
mol dm3 tetrabutylammonium tetrafluoroborate as supporting electrolyte
(44). Reversible electrochromism was achieved only when the cell gap was kept
at 0.28 mm. On/off application of 1.0 V was sufficient to observe the color
change.
https://www.youtube.com/watch?v=oVN9DV1LmSU
https://www.youtube.com/watch?v=mF_Z8RUZjJE
http://jp.ricoh.com/technology/tech/pdf/EP1-1.pdf
http://pubs.acs.org/doi/ipdf/10.1021/am404226e
http://www.investigacionyciencia.es/revistas/investigacion-yciencia/numero/447/materiales-electrocrmicos-11627
http://ac.els-cdn.com/S1386142515000177/1-s2.0-S1386142515000177main.pdf?_tid=b196d328-e919-11e4-898a00000aacb362&acdnat=1429725909_d36becc5566aa41e4e08d4f37d29d52e
http://0-pubs.acs.org.millenium.itesm.mx/doi/abs/10.1021/am301213b
http://0-pubs.acs.org.millenium.itesm.mx/doi/abs/10.1021/cm1021245
http://0-pubs.acs.org.millenium.itesm.mx/doi/abs/10.1021/am404226e