Dr. Sabine Barbara Heusing

The paper reports first on the electrochemical behavior in liquid Li+ electrolytes of 200 nm thick single sol-gel (CeO2)0.81-TiO2 electrochromic (EC) layers deposited by the dip-coating process. The electrolytes were solutions of 1 M LiCO4 dissolved in dry propylene carbonate (PC) (containing 0.03wt% of water) and wet PC containing up to 10wt% of water, respectively. Then an electrochemical quartz crystal microbalance was used as a sensitive detector to analyze the mass changes occurring during the Li+ ion exchange processes. These electrochemical processes were studied for 370 nm thick double layers, deposited on gold-coated quartz crystal electrodes and sintered at 450 °C in air. The electrolytes were the same solutions with water content varying from 0.03 up to 3wt% of water. The processes have been studied in the potential range from -2.0 to + 1.0 V vs. Ag/AgClO4 during 100 voltammetry cycles. The composition of the (CeO2)0.81-TiO2 layers was found to change during the early cycles, mainly because of an irreversible Li+ intercalation. It was found, however, that the mass change observed during cycling is not due only to a pure Li+ ion exchange process but also involves the adsorption/desorption or exchange of other cations and anions contained in the electrolyte. These ions are Li+ and ClO4- in dry electrolyte and Li+, hydrated Li(H2O)n+ and ClO4- in wet electrolyte. The improvement of the reversibility of the intercalation and deintercalation processes as well as the faster kinetics observed in wet electrolytes are finally discussed in terms of a model in which the formation of hydrated Li+ ions takes an important role.

Pure and doped niobium oxide (Nb2O5) layers are electrochromic (EC) materials which change their color by insertion of Li+ ions from transparent to brown, grey or blue depending on the crystallinity of the layer. EC-devices with the configuration K-glass/EC-layer/composite electrolyte/ion-storage (IS) layer/K-glass, were produced using different Nb2O5 EC-layers, a (CeO2)x(TiO2)1-x (x = 0.45) IS-layer and an inorganic-organic composite electrolyte to which a small amount of water (up to 3 wt.%) was added. The grey coloring all-solid-state sol-gel devices fabricated with Nb2O5:MO coatings show a high reversible coloration (∆OD = 0.3) and a long-term stability of more than 55000 switching cycles. Large area EC-devices (30 x 40 cm) show a transmittance change between 60% and 25% at 550 nm after galvanostatic coloration and bleaching for 3 min and a coloration efficiency of 27 cm2/C. The results obtained with blue and brown coloring Nb2O5 EC-layers and a comparison with blue coloring WO3 layers are also presented.

This paper describes the manufacturing and spectroelectrochemical characterization of all solid electrochromic devices (ECD). Both electrochromic (WO3) and storage ion (CeO2-TiO2) thin films were obtained by sol-gel method and deposited by dip-coating technique. The electrolytes were obtained by plasticization of starch with glycerol and addition of LiClO4 salt. The spectroelectrochemical measurements were performed with the complete devices as a function of the applied potential. The obtained results revealed that the color/bleaching process was reversible and the inserted/extracted charge was about 4.6 mC/cm2 for the applied potential of -2.0 V and increased up to 5.3 mC/cm2 for -2.3 V. This value was stable up to -2.5 V applied. The transmittance change at 630 nm was about 30% for 2.3 V applied and the optical density was about 0.25. The memory tests showed that the colored device bleached completely in open circuit in about 500 min. All the obtained results show that the presented devices are very good candidates to be tested as smart windows for architectural applications.

Films of NiO-TiO2 with Ni concentration of 100, 90, 87, 83, 75, 66, 50 and 33 mol% have been obtained via the sol-gel route by dip coating technique and sintered in air between 250 and 500°C using ethanolic sols of nickel acetate tetrahydrate (Ni(CH3COO)2∙4H2O) and titanium n-propoxide (Ti(O-CH(CH3)2)4) precursors. Xerogels obtained by drying the sols have been studied up to 900°C by thermal analysis (DTA/TG) coupled to mass and IR spectroscopy. The crystalline structure and morphology of the layers in the as deposited, bleached and colored states were determined by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy. Their electrochromic properties have been studied in 1 M KOH aqueous electrolyte as a function of the layer composition, thickness and sintering temperature. Deep brown colour with reversible transmittance changes have been obtained using cycling voltammetry and chronoamperometry processes. The best composition to get stable sols, a high reversible transmittance change and fast switching times (< 10 s) was obtained with double NiO-TiO2 layers 160 nm thick having 75% Ni molar concentration, and sintered between 300 and 350°C. The mechanism of coloration and morphology transformation of the layer during cycling are discussed in terms of an activation and degradation period. The results are in agreement with the accepted Bode model.