[en] The intercalation and de-intercalation of lithium cations in electrochromic tungsten oxide thin films are significantly influenced by their structural and surface characteristics.
In this study, we prepared two types of amorphous films via the sol-gel technique: one dense and one mesoporous in order to compare their response upon lithium intercalation and de-intercalation.
According to chronoamperometric measurements, Li+ intercalates/de-intercalates faster in the mesoporous film (24s/6s) than in the dense film (48s/10s). The electrochemical measurements (cyclic voltammetry and chronoamperometry) also showed worse reversibility for the dense film compared to the mesoporous film, giving rise to important Li+ trapping and remaining coloration of the film. Raman analysis showed that the mesoporous film provides more accessible and various W-O surface bonds for Li+ intercalation. On the contrary, in the first electrochemical insertion and de-insertion in the dense film, Li+ selectively reacts with a few surface W-O bonds and preferentially intercalates into pre-existing crystallites to form stable irreversible LixWO3 bronze.
J. Shieh, H.M. Feng, M.H. Hon, and H.Y. Juang WO3 and W-Ti-O thin-film gas sensors prepared by sol-gel dip-coating Sensors and Actuators, B: Chemical B86 2002 75 80
S.-H. Baeck, K.-S. Choi, T.F. Jaramillo, G.D. Stucky, and E.W. McFarland Enhancement of photocatalytic and electrochromic properties of electrochemically fabricated mesoporous WO3 thin films Advanced Materials (Weinheim, Germany) 15 2003 1269 1273
B. Yang, Y. Zhang, E. Drabarek, P.R.F. Barnes, and V. Luca Enhanced Photoelectrochemical Activity of Sol-Gel Tungsten Trioxide Films through Textural Control Chemistry of Materials 19 2007 5664 5672 (Pubitemid 350150596)
J. Livage, and D. Ganguli Sol-gel electrochromic coatings and devices: A review Solar Energy Materials & Solar Cells 68 2001 365 381 (Pubitemid 32263631)
C.G. Granqvist Handbook of Inorganic Electrochromic Materials 1995 Elsevier Science
R. Baetens, B.P. Jelle, and A. Gustavsen Properties, requirements and possibilities of smart windows for dynamic daylight and solar energy control in buildings: A state-of-the-art review Solar Energy Materials and Solar Cells 94 2010 87 105
A.K. Srivastava, M. Deepa, S. Singh, R. Kishore, and S.A. Agnihotry Microstructural and electrochromic characteristics of electrodeposited and annealed WO3 films Solid State Ionics 176 2005 1161 1168 (Pubitemid 40424376)
H. Zheng, J.Z. Ou, M.S. Strano, R.B. Kaner, A. Mitchell, and K. Kalantar-zadeh Nanostructured Tungsten Oxide-Properties, Synthesis, and Applications Advanced Functional Materials 21 2011 2175 2196
J.V. Gabrusenoks, P.D. Cikmach, A.R. Lusis, J.J. Kleperis, and G.M. Ramans Electrochromic colour centres in amorphous tungsten trioxide thin films Solid State Ionics 14 1984 25 30 (Pubitemid 14673532)
O. Pyper, A. Kaschner, and C. Thomsen In situ Raman spectroscopy of the electrochemical reduction of WO3 thin films in various electrolytes Solar Energy Materials and Solar Cells 71 2002 511 522 (Pubitemid 34040625)
P.R. Bueno, F.M. Pontes, E.R. Leite, L.O.S. Bulhões, P.S. Pizani, P.N. Lisboa-Filho, and W.H. Schreiner Structural analysis of pure and LiCF3SO3-doped amorphous WO3 electrochromic films and discussion on coloration kinetics Journal of Applied Physics 96 2004 2102 2109
B. Orel, U.O. Krasovec, N. Groselj, M. Kosec, G. Drazic, and R. Reisfeld Gasochromic behavior of sol-gel derived Pd doped peroxopolytungstic acid (W-PTA) nano-composite films J. Sol-Gel Sci. Technol. 14 1999 291 308
P. Delichere, P. Falaras, M. Froment, A. Hugot-Le Goff, and B. Agius Electrochromism in anodic WO3 films I: Preparation and physicochemical properties of films in the virgin and coloured states Thin Solid Films 161 1988 35 46 (Pubitemid 18660775)
J.L. Paul, and J.C. Lassègues Infrared Spectroscopic Study of Sputtered Tungsten Oxide Films Journal of Solid State Chemistry 106 1993 357 371
B. Orel, N. Grošelj, U.O. Krašovec, R. Ješe, and A. Georg IR Spectroscopic Investigations of Gasochromic and Electrochromic Sol-Gel - Derived Peroxotungstic Acid/Ormosil Composite and Crystalline WO3 Films Journal of Sol-Gel Science and Technology 24 2002 5 22 (Pubitemid 34515386)
G. Leftheriotis, S. Papaefthimiou, and P. Yianoulis The effect of water on the electrochromic properties of WO3 films prepared by vacuum and chemical methods Solar Energy Materials & Solar Cells 83 2004 115 124
J.G. Zhang, D.K. Benson, C.E. Tracy, S.K. Deb, A.W. Czanderna, and C. Bechinger Chromic Mechanism in Amorphous WO3 Films Journal of the Electrochemical Society 144 1997 2022 2026 (Pubitemid 127585337)
T. Ohtsuka, N. Goto, and N. Sato Change of the anodic oxide films of tungsten during the electrochromic reaction Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 287 1990 249 264 (Pubitemid 20733079)
S.-H. Lee, H.M. Cheong, C. Edwin Tracy, A. Mascarenhas, R. Pitts, G. Jorgensen, and S.K. Deb Influence of microstructure on the chemical diffusion of lithium ions in amorphous lithiated tungsten oxide films Electrochimica Acta 46 2001 3415 3419 (Pubitemid 32748567)
N. Sharma, M. Deepa, P. Varshney, and S.A. Agnihotry FT-IR and absorption edge studies on tungsten oxide based precursor materials synthesized by sol-gel technique Journal of Non-Crystalline Solids 306 2002 129 137 (Pubitemid 34624093)
W. Wang, Y. Pang, and S.N.B. Hodgson Preparation, characterisation and electrochromic property of mesostructured tungsten oxide films via a surfactant templated sol-gel process from tungstic acid Journal of Sol-Gel Science and Technology 54 2010 19 28
J.-H. Choy, Y.-I. Kim, J.-B. Yoon, and S.-H. Choy Temperature-dependent structural evolution and electrochromic properties of peroxopolytungstic acid J. Mater. Chem. 11 2001 1506 1513 (Pubitemid 32436549)
W. Cheng, E. Baudrin, B. Dunn, and J.I. Zink Synthesis and electrochromic properties of mesoporous tungsten oxide Journal of Materials Chemistry 11 2001 92 97 (Pubitemid 32066100)
S. Sallard, T. Brezesinski, and B.M. Smarsly Electrochromic Stability of WO3 Thin Films with Nanometer-Scale Periodicity and Varying Degrees of Crystallinity The Journal of Physical Chemistry C 111 2007 7200 7206 (Pubitemid 46854585)
M. Deepa, T.K. Saxena, D.P. Singh, K.N. Sood, and S.A. Agnihotry Spin coated versus dip coated electrochromic tungsten oxide films: Structure, morphology, optical and electrochemical properties Electrochim. Acta 51 2006 1974 1989 (Pubitemid 43133111)
J. Nagai, T. Kamimori, and M. Mizuhashi Electrochromism in amorphous lithium tungsten oxide films Solar Energy Materials 13 1986 279 295 (Pubitemid 16548386)
J.G. Zhang, C.E. Tracy, D.K. Benson, and S.K. Deb The influence of microstructure on the electrochromic properties of lithium tungsten oxide (LixWO3) thin films. Part I. Ion diffusion and electrochromic properties J. Mater. Res. 8 1993 2649 2656
T.J. Vink, E.P. Boonekamp, R.G.F.A. Verbeek, and Y. Tamminga Lithium trapping at excess oxygen in sputter-deposited a-WO3 films J. Appl. Phys. 85 1999 1540 1544 (Pubitemid 129614947)
S.-H. Lee, H.M. Cheong, C.E. Tracy, A. Mascarenhas, J.R. Pitts, G. Jorgensen, and S.K. Deb Alternating current impedance and Raman spectroscopic study on electrochromic a-WO3 films Applied Physics Letters 76 2000 3908 3910
A. Baserga, V. Russo, F. Di Fonzo, A. Bailini, D. Cattaneo, C.S. Casari, A. Li Bassi, and C.E. Bottani Nanostructured tungsten oxide with controlled properties: Synthesis and Raman characterization Thin Solid Films 515 2007 6465 6469 (Pubitemid 46660902)
S.-H. Lee, H.M. Cheong, C.E. Tracy, A. Mascarenhas, D.K. Benson, and S.K. Deb Raman spectroscopic studies of electrochromic a-WO3 Electrochimica Acta 44 1999 3111 3115
B.M. Weckhuysen, J.-M. Jehng, and I.E. Wachs In Situ Raman Spectroscopy of Supported Transition Metal Oxide Catalysts: 18O2- 16O2 Isotopic Labeling Studies The Journal of Physical Chemistry B 104 2000 7382 7387
W. Weltner Jr., and D. McLeod Jr. Spectroscopy of tungsten oxide molecules in neon and argon matrices at 4° and 20°K Journal of Molecular Spectroscopy 17 1965 276 299
M.F. Daniel, B. Desbat, J.C. Lassegues, B. Gerand, and M. Figlarz Infrared and Raman study of WO3 tungsten trioxides and WO3.xH 2O tungsten trioxide hydrates Journal of Solid State Chemistry 67 1987 235 247 (Pubitemid 17574267)
S.-H. Lee, H.M. Cheong, C.E. Tracy, A. Mascarenhas, A.W. Czanderna, and S.K. Deb Electrochromic coloration efficiency of a-WO3-y thin films as a function of oxygen deficiency Applied Physics Letters 75 1999 1541 1543 (Pubitemid 129562403)
M. Deepa, A.G. Joshi, A.K. Srivastava, S.M. Shivaprasad, and S.A. Agnihotry Electrochromic Nanostructured Tungsten Oxide Films by Sol-gel: Structure and Intercalation Properties Journal of the Electrochemical Society 153 2006 C365 C376
