01524nas a2200157 4500008004100000050001500041245011400056210006900170260003600239490000600275520094200281100001901223700002401242700002701266856007301293 2008 eng d aLBNL-1089E00aElectrochromically switched, gas-reservoir metal hydride devices with application to energy-efficient windows0 aElectrochromically switched gasreservoir metal hydride devices w aEindhoven, Netherlandsc08/20030 v13 a

Proof-of-principle gas-reservoir MnNiMg electrochromic mirror devices have been investigated. In contrast to conventional electrochromic approaches, hydrogen is stored (at low concentration) in the gas volume between glass panes of the insulated glass units (IGUs). The elimination of a solid state ion storage layer simplifies the layer stack, enhances overall transmission, and reduces cost. The cyclic switching properties were demonstrated and system durability improved with the incorporation a thin Zr barrier layer between the MnNiMg layer and the Pd catalyst. Addition of 9% silver to the palladium catalyst further improved system durability. About 100 full cycles have been demonstrated before devices slow considerably. Degradation of device performance appears to be related to Pd catalyst mobility, rather than delamination or metal layer oxidation issues originally presumed likely to present significant challenges.

1 aAnders, André1 aSlack, Jonathan, L.1 aRichardson, Thomas, J. uhttps://facades.lbl.gov/publications/electrochromically-switched-gas01729nas a2200145 4500008004100000050001500041245004700056210004700103260002900150520125500179100002701434700002401461700002301485856007501508 2000 eng d aLBNL-4651000aElectrochromism in Copper Oxide Thin Films0 aElectrochromism in Copper Oxide Thin Films aUppsala, Swedenc08/20003 a

Transparent thin films of copper(I) oxide prepared on conductive SnO2:F glass substrates by anodic oxidation of sputtered copper films or by direct electrodeposition of Cu2O transformed reversibly to opaque metallic copper films when reduced in alkaline electrolyte. In addition, the same Cu2O films transform reversibly to black copper(II) oxide when cycled at more anodic potentials. Copper oxide-to-copper switching covered a large dynamic range, from 85% and 10% photopic transmittance, with a coloration efficiency of about 32 cm2/C. Gradual deterioration of the switching range occurred over 20 to 100 cycles. This is tentatively ascribed to coarsening of the film and contact degradation caused by the 65% volume change on conversion of Cu to Cu2O. Switching between the two copper oxides (which have similar volumes) was more stable and more efficient (CE = 60 cm2/C), but covered a smaller transmittance range (60% to 44% T). Due to their large electrochemical storage capacity and tolerance for alkaline electrolytes, these cathodically coloring films may be useful as counter electrodes for anodically coloring electrode films such as nickel oxide or metal hydrides.

1 aRichardson, Thomas, J.1 aSlack, Jonathan, L.1 aRubin, Michael, D. uhttps://facades.lbl.gov/publications/electrochromism-copper-oxide-thin01659nas a2200193 4500008004100000050001500041245009400056210006900150260002500219520098200244100002301226700002301249700002101272700002501293700002701318700002401345700002101369856007501390 1998 eng d aLBNL-4227700aEffect of Hydrogen Insertion on the Optical Properties of PD-Coated Magnesium Lanthanides0 aEffect of Hydrogen Insertion on the Optical Properties of PDCoat aLondon, U.K.c9/19983 a

Metallic magnesium lanthanide thin films upon insertion of hydrogen transform to a highly transparent hydride phase. With a Pd overlayer, the transformation can be produced either by electrochemical insertion of hydrogen or by exposing the film to hydrogen gas. Unlike amorphous oxide electrochromics, the transformation is accompanied by a large change in visible reflectance (about 50%). The optical switching effect in these materials is investigated in terms of changes in the complex refractive index as determined by variable-angle spectroscopic ellipsometric and normal-incidence radiometric measurements over the solar spectrum. Furthermore the optical effect of converting the Pd caplayer to Pd-H was determined. It is shown that the pd layer limits the visible transmittance of the hyrdrided stack to about 35-40%. Whereas the extinction coefficient of the dehydrided LnMg-layers at 550 nm is between 2.2 and 3.1, it is as low as 10-4 in the transparent state.

1 avon Rottkay, Klaus1 aRubin, Michael, D.1 aMichalak, Franck1 aArmitage, Robert, D.1 aRichardson, Thomas, J.1 aSlack, Jonathan, L.1 aDuine, Peter, A. uhttps://facades.lbl.gov/publications/effect-hydrogen-insertion-optical02282nas a2200229 4500008004100000245008200041210006900123260001200192300001000204490000700214520155300221653002501774653002801799653001501827100002301842700001701865700002701882700001901909700002301928700002401951856007701975 1998 eng d00aElectrochromic lithium nickel oxide by pulsed laser deposition and sputtering0 aElectrochromic lithium nickel oxide by pulsed laser deposition a c07/1998 a59-660 v543 a

Thin films of lithium nickel oxide were deposited by sputtering and pulsed laser deposition (PLD) from targets of pressed LiNiO2 powder. The composition and structure of these films were analyzed using a variety of techniques, such as nuclear-reaction analysis, Rutherford backscattering spectrometry (RBS), X-ray diffraction, infrared spectroscopy, and atomic-force microscopy. Crystalline structure, surface morphology and chemical composition of LixNi1−xO thin films depend strongly on deposition oxygen pressure, temperature as well as substrate–target distance. The films produced at temperatures lower than 600°C spontaneously absorb CO2 and H2O at their surface once they are exposed to the air. The films deposited at 600°C proved to be stable in air over a long period. Even at room temperature the PLD films are denser and more stable than sputtered films. RBS determined the composition of the best films to be Li0.5Ni0.5O deposited by PLD at 60 mTorr O2 pressure. Electrochemical tests show that the films exhibit excellent reversibility in the range 1.0–3.4 V versus lithium. Electrochemical formatting which is used to develop electrochromism in other films is not needed for the stoichiometric films. The optical transmission range is almost 70% at 550 nm for 150 nm-thick films. Devices made from these films were analyzed using novel reference electrodes and by disassembling after cycling.

10aLithium nickel oxide10apulsed laser deposition10asputtering1 aRubin, Michael, D.1 aWen, Shi-Jie1 aRichardson, Thomas, J.1 aKerr, John, B.1 avon Rottkay, Klaus1 aSlack, Jonathan, L. uhttps://facades.lbl.gov/publications/electrochromic-lithium-nickel-oxide01510nas a2200181 4500008004100000050001500041245010000056210006900156300001400225490000700239520088500246100002101131700002301152700002701175700002401202700002301226856007901249 1998 eng d aLBNL-4227600aElectrochromic Lithium Nickel Oxide Thin Films by RF-Sputtering from a LiNiO2 Target0 aElectrochromic Lithium Nickel Oxide Thin Films by RFSputtering f a3085-30920 v443 a

Thin films of lithium nickel oxide were deposited by rf sputtering from a stoichiometric LiNiO2 target. The composition and structure of these films depended on the oxygen pressure during deposition (sputtering gas is Argon), and, to a certain extent, the target history. The sputtering geometry, i.e. the substrate to target distance and the sputtering angle were also critical. the films exhibit excellent reversibility in the potential range 1.1V to 3.8 V vs Li/Li+ and could be cycled in a liquid electrolyte half cell for more than 3000 cycles with a switching range ΔTvis close to 70%. The coloration efficiency in the visible was typically -30 to -40 cm2 C-1. The switching performance of a device utilizing a lithium nickel oxide film as counter electrode for a tungsten oxide electrochromic film is reported.

1 aMichalak, Franck1 avon Rottkay, Klaus1 aRichardson, Thomas, J.1 aSlack, Jonathan, L.1 aRubin, Michael, D. uhttps://facades.lbl.gov/publications/electrochromic-lithium-nickel-oxide-102057nas a2200229 4500008004100000050001500041245011100056210006900167260002700236300001100263490000900274520128000283653002601563653002801589653001901617653002201636100002301658700002701681700002301708700002401731856007201755 1997 eng d aLBNL-4066800aEffective Medium Approximation of the Optical properties of electrochromic cerium-titanium oxide compounds0 aEffective Medium Approximation of the Optical properties of elec aSan Diego, CAc07/1997 a19-Sep0 v31383 a

Cerium titanium oxide samples derived from a solution have been compared against sputtered films over a wide range of different compositions. X-ray diffraction was used to investigate the structural properties of the compound material existing in a two-phase mixture MAO2-MBO2. The optical properties were evaluated over the whole solar spectrum by variable angle spectroscopic ellipsometry combined with spectrophutometry. The spectral complex refractive index was determined for CeO2 and TiO2, as well as for their compounds. To reduce the large number of permutations in composition of multi-component oxides it would be useful to be able to predict the properties of the mixtures from the pure oxide components. Therefore these results were compared to those obtained by effective medium theory utilizing the optical constants of CeO2 and TiO2. In order to investigate the performance as passive counter-electrode in Li+ based electrochromic devices the films were tested by cyclic voltammetry with in-situ transmission control. Chemical composition was measured by Rutherford backscattering spectrometry. Surface morphology was analyzed by atomic force microscopy.

10acerium titanium oxide10aeffective medium theory10aelectrochromic10aoptical constants1 avon Rottkay, Klaus1 aRichardson, Thomas, J.1 aRubin, Michael, D.1 aSlack, Jonathan, L. uhttps://facades.lbl.gov/publications/effective-medium-approximation