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    • 专利摘要:
    The present invention relates to an electrochromic device comprising an electrode doped with a conductive metal level and chemically adsorbing an electroactive compound to contain an optically modified nanostructured metal oxide film. The electrochromic device is suitable for applications requiring optical modulation such as a wide static display and an automatic photosensitive rear mirror. The present invention also relates to nanostructured metal oxide films suitable for use in electrochromic devices and electrodes comprising same.
    公开号:KR20020062286A
    申请号:KR1020027004478
    申请日:2000-10-11
    公开日:2002-07-25
    发明作者:도널드 피츠마우리스；다비드 커민스；다비드 코르；나가라자 에스. 라오；게리트 보쉬루
    申请人:유니버시티 칼리지 더블린；
    IPC主号:
    专利说明:

    ELECTROCHROMIC DEVICE
    [1] The present invention relates to a electrochromic device. In particular, the present invention relates to a nanostructured metal oxide film modified by chemically adsorbing an electroactive compound doped with a conductive metal level, an electrode comprising the nanostructured film, and an electrochromic device comprising the electrode.
    [2] The use of electrochromic devices is well known in applications where optical modulation is required, such as broad static markers and auto-dimming rearview mirrors. For example, as shown in WO-A-97/35227 and WO-A-98/35267, electrochromatography comprising one or more electrodes combined with a semiconducting nanostructured metal oxide film modified by chemically adsorbing electroactive compounds Devices are also known.
    [3] The device described in WO-A-97/35227 comprises an n-or p-type redox chromophore chemisorbed on the surface of a nanostructured semiconductor electrode, and a p- or n-type auxiliary which can be reversibly oxidized or reduced The electroactive compound is dissolved in each electrolyte. In the apparatus described in WO-A-98/35267, the n-type redox chromophore is chemisorbed onto the surface of the nanostructured semiconductor and the p-type redox promoter is dissolved in the electrolyte. The switching time of the device is faster than the switching time of a previously known device, but is still relatively slow due to the rate-limiting step that the electroactive compound in the electrolyte diffuses to the associated electrode. Although attempts have been made to remove the rate-determining step by adsorbing the compound on the electrode to which the compound should be diffused, the switching rate can only be increased to some extent due to the semiconductive nature of the nanostructured substrate.
    [4] The devices described in WO-A-97/35227 and WO-A-98/35267 are suitable for the above mentioned applications, but faster switching times are particularly desirable for applications involving dynamic markers, privacy glazing and high performance windows will be.
    [5] It is an object of the present invention to avoid or reduce the disadvantages of the prior art. It is also an object of the present invention to provide an electrochromic device having a faster switching time than known devices.
    [6] According to the present invention, there is provided a nano-porous nano-microcrystalline film containing an electroconductive metal oxide containing an electroactive compound, wherein the electroactive compound is a p-type or n-type redox promoter or a p- Type or n-type redox chromophore.
    [7] The " nano-microcrystalline film " is composed of molten nanometer-sized microcrystals. The microcrystallization is appropriately doped to produce a conductive film. In " nanoporous nano-microcrystalline " membranes, the shape of the molten nano-microcrystals is nanometer-sized porous. The film, which can be referred to herein as a (conductive / semiconductive) nanostructured film, is typically about 3 microns in thickness and about 1000 in surface roughness. The conductive nanostructured film has a resistance of 20 kOhm / square at room temperature in the case of a 3 탆 nanostructured antimony film doped with SnO 2 on a nonconductive substrate.
    [8] As used herein, the term " conductive metal oxide " refers to a metal oxide suitably doped to a level of less than 10 Kohms / square with a resistance of the metal oxide thin plate.
    [9] As used herein, the term " electroactive compound " refers to (1) a compound that is adsorbed and oxidized on the surface of a conductive nanostructured metal oxide film. When the compounds discolor when oxidized, they are referred to as p-type redox chromophore. If they do not change color, they are called p-type redox promoters. ; And (2) adsorbed and reduced on the surface of semiconductive or conductive nanostructured metal oxide. When the compound is discolored when it is reduced, it is called an n-type redox chromophore. If they do not change color, they are called n-type redox promoters.
    [10] The present invention also provides an electrode comprising an electrically conductively coated transparent or translucent substrate for use in an electrochromic device, the substrate having a conductive nanostructured metal oxide film in accordance with the present invention.
    [11] The present invention further provides an electrochromic device comprising at least one electrode according to the present invention.
    [12] The electrochromic device of the present invention may include two electrodes, each electrode comprising a conductive nanostructured metal oxide film in accordance with the present invention.
    [13] Thus, one embodiment of the present invention is a method
    [14] (a) a nano-structured film containing an n-type or p-type redox chromophore or an n-type or p-type redox promoter adsorbed on an electrode and comprising a conductive metal oxide is electrically Or a semitransparent substrate;
    [15] (b) a nanostructured film containing a p-type or n-type redox promoter or a p-type or n-type redox chromophore absorbed in the electrode and containing a conductive metal oxide is transparent Or a second or opposite electrode comprising a translucent substrate; And
    [16] (c) the electrolyte between the electrodes.
    [17] Which is an electrochromic device.
    [18] In a preferred embodiment,
    [19] (a) a first electrode comprising a transparent or semitransparent substrate comprising a nano-structured film containing an n-type redox chromophore adsorbed on an electrode and comprising a semiconductive metal oxide electrically conductively coated inside the electrode;
    [20] (b) a second or opposite electrode comprising a transparent or semitransparent substrate containing a p-type redox promoter adsorbed on the electrode and having a nanostructured film comprising a conductive metal oxide electrically coated within the electrode; And
    [21] (c) the electrolyte between the electrodes.
    [22] In the electrochromic device according to the present invention.
    [23] Alternatively, the p-type redox chromophore may be adsorbed to the conductive metal oxide and then the n-type redox promoter may be adsorbed to the semiconductive metal oxide.
    [24] In a particularly preferred embodiment of the electrochromic device of the present invention, the first electrode is a cathode and the nanostructured film coated on the negative electrode contains an n-type redox chromophore of Formula I, II or III (described herein) which comprises TiO 2. And the second electrode is an anode and the nanostructured film coated on the anode comprises SnO 2 : Sb containing a p-type redox promoter of formula IV, V or VI (described herein) adsorbed on the anode.
    [25] In yet another aspect,
    [26] (a) a first electrode comprising a transparent or semitransparent substrate comprising a nano-structured film containing an n-type or p-type redox chromophore that is adsorbed to an electrode and comprising a conductive or semi- ;
    [27] (b) a second or opposite electrode comprising a transparent or semitransparent substrate in which there is no electroactive compound adsorbed on the electrode and the nanostructured film comprising a conductive metal oxide is electrically conductively coated inside the electrode; And
    [28] (c) the electrolyte between the electrodes.
    [29] And an electrochromic device.
    [30] In this embodiment, the device will operate as an electrochromic device due to the physical nature of the nanostructured film. First, the material can release redox chromophore on the (semiconductive) -conductive metal oxide electrode by emitting and providing electrons, and secondly, because of the high film roughness, the interface between the electrolyte and the membrane is maintained, The effective charge replenishment can be continued. If the device has a smooth membrane, its performance will be less effective.
    [31] The electrochromic device of the present invention comprises:
    [32] (1) when the metal oxide is a semiconductive metal oxide, the n-type electroactive compound is adsorbed on the oxide;
    [33] (2) both the first and second electrodes comprise an electroactive compound: (a) the first electrode comprises an n-type redox chromophore and the second electrode comprises a p-type redox promoter or vice versa. ; Or (b) the first electrode comprises an n-type redox promoter and the second electrode comprises a p-type redox chromophore or vice versa. ; (a) and (b) are subject to (1) above;
    [34] (3) When only one of the first and second electrodes contains an electroactive compound, the compound is an n-type or p-type redox chromophore under the condition of (1) above.
    [35] .
    [36] Preferably, the electrodes in the electrochromic device of the present invention are spaced apart from each other by an interval of 5 mm or more, preferably 50 m to 5 mm, for example.
    [37] Suitable n- or p-type redox promoters or redox chromophores may be used in the conductive nanostructured films of the present invention.
    [38] Preferred p-type redox promoters and redox chromophore are compounds of the following formula IV-VII.
    [39]
    [40]
    [41] Wherein X in formula (V) is S or O and R 8 -R 10 are each independently selected from the group consisting of
    [42] Selected:
    [43]
    [44] Wherein R 11 is C 1-10 alkyl and R 12 -R 15 are each independently hydrogen; C 1-10 alkyl; C 1-10 alkylene; Optionally substituted aryl; halogen; Nitro; Or an alcohol group, and n = 1 - 10.
    [45] The compounds of general formula V, VI and VII are novel and form part of the present invention, together with their use in the preparation of conductive nanostructured membranes, electrodes and electrochromic devices by the present invention.
    [46] Compounds of formula (IV) are known and described in J. Am. Chem. Soc. 1999, < RTI ID = 0.0 > 121 , 1324-1336. ≪ / RTI >
    [47] Compounds of formula V may be prepared by reacting phenothiazine with an alkyl halide terminated with a precursor or with a suitable bond group.
    [48] Can be prepared by reacting a compound of formula VI with an alkyl halide terminated with a precursor or a suitable linking group, with alkyl substituted by dihydro-dialkyl phenazines.
    [49] Can be prepared by reacting a compound of formula VII with an appropriately derived ferrocene with an alkyl halide terminated with a precursor or with a suitable bond group.
    [50] A particularly preferred p-type redox promoter of the general formula V is - (10-phenothiazyl) propoxyphosphonic acid. This compound (Compound VIII) can be prepared according to Reaction Scheme 1 herein.
    [51] The conductive metal oxide used in the nanostructured film of the present invention is preferably selected from the following:
    [52] (a) SnO 2 doped with F, Cl, Sb, P, As or B;
    [53] (b) ZnO doped with Al, In, Ga, B, F, Si, Ge, Ti, Zr or Hf;
    [54] (c) In 2 O 3 doped with Sn;
    [55] (d) CdO;
    [56] (e) ZnSnO 3, Zn 2 In 2 O 5, In 4 Sn 3 O 12, GaInO 3 or MgIn ternary oxide, such as 2 O 4;
    [57] (f) Sb and doped Fe 2 O 3 ;
    [58] (g) TiO 2 / WO 3 or TiO 2 / MoO 3 systems; And
    [59] (h) Fe 2 O 3 / Sb or SnO 2 / Sb system.
    [60] And the Sb-doped SnO 2 are particularly preferred.
    [61] Preferred semiconductive metal oxides that can be used in the electrochromic device of the present invention are titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, iron (Fe 2+ or Fe 3+ ) Or nickel or perovskite thereof. TiO 2, WO 3 , MoO 3, ZnO and SnO 2 are particularly preferred.
    [62] A preferred n-type redox chromophore or redox promoter that can be used in the electrochromic device of the present invention is represented by the following general formula I-III:
    [63]
    [64] Wherein R 1 is selected from the following:
    [65]
    [66]
    [67] R 2 is selected from C 1-10 alkyl, N-oxide, dimethylamino, acetonitrile, benzyl optionally mono- or di-substituted with nitro and phenyl;
    [68] R 3 is C 1-10 alkyl and R 4 - R 7 is hydrogen; C 1-10 alkyl; C 1-10 alkylene; Aryl or substituted aryl; halogen; Nitro; Or an alcohol group;
    [69] X is a charge balance ion that is preferably selected from chloride, bromide, iodide, BF 4 - , PF 6 - , and ClO 4 - , and n = 1-10.
    [70] Compounds of formula (I), (II) and (III) are known and can be prepared by known methods as described in Solar Energy Materials and Solar Cells, 57 , (1999), 107-125.
    [71] A particularly preferred n-type redox chromophore for use in the present invention is a compound of formula I, i.e., bis- (2-phosphonoethyl) -4,4'-bipyridinium dichloride.
    [72] Conductive and semiconductive metal oxide films can be treated by exposure to an aqueous plasma stream prior to adsorption of the electroactive compound. This treatment is useful for promoting the reaction of a bonding group, particularly a siloxane group, of an electroactive compound containing a hydroxyl group on the surface of the metal oxide film, by increasing the concentration of the hydroxyl group. This treatment also increases the stability of the nanostructured film.
    [73] The electrode substrate is suitably formed of glass or plastic material. Glass coated with a fluorine conductive layer doped with tin oxide or indium tin oxide is easily used in the electrochromic device of the present invention.
    [74] The electrolyte used in the present invention preferably comprises one or more electrochemically inactive salts which are liquid and preferably dissolved in a solvent. Suitable salts include, for example, lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium iodide (LI), lithium hexafluorophosphate (LiPF 6 ), lithium hexafluoroarsenate 6), lithium styryl sulfonate (LiSS), lithium triflate (LiCF 3 SO 3), lithium methacrylate, LI addition of lithium chloride (LiCl), acetate with lithium bromide (LiBr) and lithium trifluoroacetate (CF 3 COOLi ), And combinations thereof. Of these, LiClO 4 or a combination of LiClO 4 and LiBF 4 is preferable. Such a source of alkali metal ions may be present in the electrolyte at a concentration of 0.01 - 1.0M, preferably 0.05 - 0.2M.
    [75] Suitable solvents include acetonitrile, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, 2-acetylbutyrolactone, propylene carbonate, ethylene carbonate, glycerine carbonate, tetramethylene sulfone, cyano Methyl ethyl ketone, ethyl sucrose, gamma -butyrolactone, 2-methylglutaronitrile, N, N'-dimethylformamide, 3-methylsulforan, glutaronitrile, 3-3'-oxydipropionitrile, , Cyclohexanone, benzoyl acetone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, 2-methoxyethyl ether, triethylene glycol dimethyl ether, 2-one, 1,2-butylene carbonate, glycidyl ether carbonate (such as the carbonate available from Texaco Chemical Company, Austin, Texas), and combinations thereof, and -Butyrolactone Lactone, propylene carbonate, 1,2-butylene carbonate Carbonate, it is preferred to include a combination of tetramethylene sulfone and combinations and 1,2-butylene carbonate and propylene carbonate, the propylene carbonate. gamma -butyrolactone is particularly preferable.
    [76] In the electrochromic device of the present invention containing a p-type redox promoter and a redox chromophore adsorbed on an electrode, a conductive nanostructured substrate is used in which an adsorbed p-type redox promoter and positively biased in a redox chromophore biased) substrates. As a result, the switching speed of the electrochromic device is greatly increased. Also, the advantages of adsorbed p-type redox enhancer or redox chromophore, low power consumption and extended memory are maintained.
    [77] The invention is illustrated in the following examples.
    [78] Example 1
    [79] (a) A 2.5 cm x 2.5 cm transparent nanostructured semiconductor film composed of a molten TiO 2 nano-microcrystalline having a thickness of 4 μm was immersed in a 3.3 cm × 3.3 cm fluoro (15 Ω, 0.5 μm thick, Libby-Owen Ford Tec 15). The TiO 2 dispersed colloid was prepared by hydrolyzing titanium tetraisopropoxide. The average diameter (7 nm) of the initially formed microcrystals was increased to 12 nm by heating to 200 DEG C under high pressure for 12 hours. Concentrated to a high-pressure heating the dispersion to 160g / l and Carbowax (trademark) 20000 (TiO 2 40% eq) was added to give a viscosity as a white solid. (Carbowax 20000 is an ethylene glycol polymer having an average molecular weight of 20000.) The solid film having a thickness of 4 mu m was placed on a conductive glass substrate using a screen printing technique. The resulting gel-membrane was dried in air for 1 hour, then sintered in air at 450 ° C for 12 hours and placed in a dark vacuum drying vessel. The resultant transparent nanostructured electrode had a thickness of 4 μm and a surface roughness of about 1000.
    [80] (b) An n-type redox chromophore of bis- (2-phosphonoethyl) -4,4'-bipyridinium dichloride was dissolved in water (75 ml) with 4,4'-bipyridine -2-ethyl bromo-phosphonate (15.0 g). The reaction mixture was refluxed for 72 hours and then cooled. After adding concentrated hydrochloric acid (75 ml), the reaction mixture was further refluxed for 24 hours. To obtain the product, the reaction mixture was concentrated to 50 ml, and isopropyl alcohol (200 ml) was added dropwise, followed by stirring on ice for 1 hour and filtration. The white microcrystalline product was washed with cold isopropyl alcohol and dried in air to give pure bis- (2-phosphonoethyl) -4,4'-bipyridinium dichloride (12.72 g, 84.24% yield). Bis- (2-phosphono-ethyl) -4,4 '- C, the value calculated bipyridinium dichloride (C 14 H 20 N 2 Cl 2 O 6 P 2) 37.77; H, 4.53; N, 6.29, the experimental value is C, 35.09; H, 4.49; N, 6.09. 1 H NMR (water-d 2 ): δ2.31 - 2.43 (m, 4H); δ4.68 - 4.80 (m, 4H); 8.33 (d, undecomposed meta-coupling, 4H): 8.94 (d, undecomposed meta-coupling, 4H)
    [81] (c) The TiO 2 film prepared as described above was modified by chemically adsorbing the n-type redox chromophore single layer, also prepared as described above, in aqueous solution (0.02 mol. dm -3 ) for 24 hours . Washed with distilled isopropanol, dried in air and placed in a dark vacuum drying vessel for 48 hours before use.
    [82] (d) A 2.5 cm x 2.5 cm transparent nanostructured SnO 2 : Sb film was deposited on a 3.3 cm x 3.3 cm F-doped tin oxide glass substrate (15 Ω, 0.5 μm thick, provided by Libby-Owen Ford Tec 15) of Physical Chemistry, 1999, 103, 3093-3098, G. Boschloo and D. Fitzmaurice, " Spectroscopy of Highly Doped Nanostructured Tin Dioxide Electrode ". Briefly, 10 drops of acetic acid (2.0 mol dm -3 ) was added to 50 g of Sb-doped SnO 2 nano-microcrystalline aqueous dispersion (15 wt% of SnO 2 : Sb provided by Alfa) with a diameter of 5 nm Respectively. The resulting gel was immediately diluted with water (15 ml) and heated at 200 < 0 > C for 12 hours. Carbowax 20000 (3.75 g) was added with stirring for 8 hours to obtain a yellow viscous paste which was diluted with water (10 ml) to make it suitable for spreading. This paste was spread on a conductive glass substrate using a glass rod and attached with a Scotch tape. After drying for 1 hour in air, the film was also heated in air at 450 DEG C for 12 hours. The resultant transparent nanostructured SnO 2 : Sb film had a thickness of 3.0 μm and a surface roughness of about 1000.
    [83] (e) p-type redox promoter VIII was prepared as described in Scheme 1 below.
    [84] XI: - (10-phenothiazyl) propionitrile
    [85] Triton B (0.6 ml of a 40% benzyltrimethylammonium hydroxide aqueous solution) was added dropwise to phenothiazine ( X , 50 g) in aqueous acrylonitrile (45 ml) to react vigorously. The reaction mixture was refluxed for 1 hour and cooled. The crude product obtained was recrystallized from a 30:70 mixture of ethanol and acetone to give orange XI crystals. (31.27 g, 49.6%).
    [86] XII: - (10-phenothiazyl) propionic acid
    [87] Compound XI (31.27 g) was added to a mixed solvent (350 ml of methanol, 105 ml of water) of NaOH (35 g), refluxed for 15 hours, and cooled. The crude product was poured into ice water and acidified with sulfuric acid (2 mol dm -3 ) until a white precipitate was formed. The crude product was recrystallized to obtain XII . (17.0 g, 52.26%).
    [88] XIII: - (10-phenothiazyl) propionate ester
    [89] Compound XII (17 g) was dissolved in a 1: 2 by volume mixture (700 ml) of ethanol and toluene, acidified with concentrated sulfuric acid (4 ml) and refluxed overnight. The solution was concentrated (to about 50 ml) and diluted by adding water (500 ml). The crude product was extracted with ethyl acetate (4 x 200 ml), washed with water, dried over MgSO 4 and evaporated under reduced pressure to remove the solvent. The white crystals XIII precipitated in the cooled solution. (11.85 g, 63.9%)
    [90] XIV: - (10-phenothiazyl) propanol
    [91] A solution of compound XIII (11.85 g) in dry diethyl ether (33 ml) was added dropwise to a suspension of LiAlH 4 (4.74 g) in dry diethyl ether (70 ml) and stirred overnight at room temperature. Excess LiAlH 4 was decomposed by adding water dropwise and filtered. The solvent was removed under reduced pressure to obtain a green solid XIV (5.57 g, 54.7%).
    [92] XV: - (10-phenothiazyl) propoxyphosphonic acid dichloride
    [93] A solution of XIV (1.0 g) and pyridine (1.0 ml) in dry chloroform (60 ml) was cooled to -15 < 0 > C. A solution of phosphorus oxychloride (4.73 ml), pyridine (1.0 ml) and dry chloroform (40 mls) was added dropwise over 0.5 hour. The reaction mixture was stirred at -15 [deg.] C for 2 hours and the resulting homogeneous solution was placed at ambient temperature for 1.5 hours. The chloroform was removed under reduced pressure, and the crude product was washed with toluene (3 x 50 ml) to remove unreacted phosphorus oxychloride to obtain green oil XV (0.9 g, 65.2%).
    [94] V III: - (10-phenothiazyl) propoxyphosphonic acid
    [95] The solution of XV (0.9 g) in deionized water (60 ml) was stirred overnight. The crude product was extracted with ethyl acetate (4 x 50 ml), washed with water and dried over sodium sulfate. The resulting white crystals were separated by filtration, and the filtrate was further recrystallized three times to obtain Vl III product (0.301 g, 40%).
    [96] The calculated values of V III (C 15 H 16 O 4 NSP) were C, 53.43; H, 4.76; N, 4.15; P, 9.19 or the experimental value C, 63.58; H, 5.42; N, 4.77; P, 1.86. 1 H NMR (CDCl 3 ): d 2.24 - 2.28 (t 2H, J = 6.3 Hz); d 3.67-3.70 (t, 2H, J = 6.2 Hz); d 4.09-4.12 (t, 2H, J = 6.5 Hz); d 6.91-7.19 (m, 8H). 31 P NMR (CDCl 3): d 1.69 - 1.89 (H 3 PO 4); d -11.96.
    [97] (f) nanostructured SnO 2 prepared as described above2: Sb films were prepared using the p-type redox promoterV IIIof Aqueous chloroform solution (0.02 mol dm < RTI ID = 0.0 >-3), Chemically adsorbed and modified, washed with distilled isopropanol, dried in air and allowed to stand for 24 hours before use in a dark vacuum drying vessel.
    [98] (g) A battery having an inner space of about 400 mu m was made of the modified TiO 2 film and the modified SnO 2 : Sb film prepared above using a thermoplastic plastic gasket (IPBOND 2025 manufactured by Industria Plastica Monregalese). The gasket has an opening in one corner.
    [99] (h) The sandwich structure was taken out of the modified vacuum drying vessel, immersed in the electrolyte solution while leaving it open, and then the inside of the vacuum drying vessel was filled with air. The electrolyte solution consisted of LiClO 4 (0.02 mol dm -3 ) in γ-butyrolactone. It should be noted that both LiClO 4 and γ-butyrolactone must be carefully purified and completely dried before use. Finally, the cell was sealed with a UV-curable epoxy resin.
    [100]
    [101] The reagents and conditions used in the synthesis ( VIII ) of Scheme 1 are as follows:
    [102] (a) acrylonitrile, 40% benzyltrimethylammonium hydroxide aqueous solution (Triton B), 0 C
    [103] (b) refluxing for 1 hour
    [104] (c) Methanol sodium hydroxide, refluxed for 15 hours.
    [105] (d) ethanol, concentrated H 2 SO 4 , refluxing overnight.
    [106] (e) LiAlH 4 , diethyl ether (dry)
    [107] (f) Phosphorus oxychloride, stirred at -15 < 0 > C for 2 h
    [108] (g) Stir for 1.5 hours while keeping it at ambient temperature
    [109] (h) H 2 O
    [110] Example 2
    [111] (a) Switching time of the electrochemical (EC) window
    [112] The color development rate of a 2.5 cm x 2.5 cm EC window assembled as described in Example 1 was measured by applying a 1.2 V voltage to bias the viologen-modified nanostructured TiO 2 film to the cathode of a phenothiazine-modified SnO 2 : Sb film . The color development time was defined as the time required for the transmittance to decrease to two-thirds of the difference between the decolorized state and the color-developed state of rectification-state transmission, which was about 450 ms. The decolorization rate of the same EC window was measured by reversing the polarity of the voltage across the color window. The decolorization time was defined as the time taken for the transmittance to increase to two thirds of the difference between the rheological state and the decolorized state in the color-coded state, which was about 250 ms.
    [113] As far as the inventor knows, the measured color development and bleaching time is the fastest switching time reported for EC windows in this field.
    [114] (b) Color development efficacy of EC window
    [115] 2.5 cm x 2.5 cm The peak of the EC window and the rectified current were also measured during color development and decolorization. The peak and rectified-state currents measured during color development were approximately 10 mA cm -2 and approximately 30 μm cm -2, respectively. The peak and rectified-state currents measured during decolorization were approximately 16 mA cm < 2 & gt ; and approximately 1 mu m cm < 2 & gt ;, respectively. At 550 nm, the colorimetric effect (λ) of CE as defined in Equation (1) was measured by an increasing curve slope of the charge Q in the device versus absorbance ΔA (λ). The measured CE (550 nm) was about 110 C -1 cm 2 .
    [116] [Formula (1)
    [117]
    [118] Both the peak and rectified currents are very low and the power consumption of the EC window is low suggesting that it can be a long term memory.
    [119] Regarding the power consumption, the 2.5 cm x 2.5 cm EC window produced in Example 1 will have a commutation-state current of about 30 μA in the developed state. This implies that the charge consumption rate is about 2.4 × 10 -3 Cs -1 or about 1.5 × 10 16 charge s -1 .
    [120] In relation to long term memory, when a voltage of 1.2 V is applied to the EC window for 60 seconds and the circuit is opened, the EC window is decolored in time units after the first color development. Quantitatively speaking, the absorbance of the EC window measured at 608 nm takes about 3 hours to recover to the original measured value, while the time required to increase the minimum transmittance of the developed state by 5% is 600 s.
    [121] (c) Stability of EC windows
    [122] The stability of the 2.5 cm x 2.5 cm EC window prepared in Example 1 was tested under conditions of 10,000 electrochromic cycles under ambient conditions. In each electrochromic cycle, a voltage of 1.2 V was applied for 15 s to bias the biologically modified nanostructured TiO 2 electrode to the cathode of the phenothiazine nanostructured SnO 2 : Sb electrode and to apply a voltage of 0.00 V for 15 s Respectively. The parameters used to characterize the cell performance were measured after 1, 10, 100, 1,000 and 10,000 electrochromic cycles and summarized in Table 1.
    [123]
    [124] (a) The experiment was carried out in a 2.5 cm x 2.5 cm apparatus assembled as described in Example 1 under ambient conditions.
    [125] (b) Each electrochromic cycle was subjected to a voltage of 1.2 V for 15 s to bias the viologen-modified nanostructured TiO 2 electrode to the cathode of the phenothiazine nanostructured SnO 2 : Sb electrode, and for 15 s And a voltage of 0.00 V was applied.
    [126] Another aspect of stability is the period during which the EC window can be maintained in a green state. The stability was measured by applying a 1.2 V voltage to bias the viologen-modified nanostructured TiO 2 electrode to the cathode of the phenothiazine-modified SnO 2 : Sb electrode, which caused the device to have a color. The required time to increase the minimum transmittance by 5% was measured as 180s, and this voltage was applied for 15s every 180s. This was maintained in the EC window throughout the color development state. It was found that the signal did not decrease after 500 hours.
    [127] In general, the summarized findings confirm that the same window is stable in the chromogenic state for 500 hours, whereas the findings summarized in Table 1 show that a 2.5 cm x 2.5 cm device assembled as described in Example 1, It is confirmed that even if the number of electrochromic cycles is 10,000 or more, it is relatively stable.
    [128] Example 3
    [129] Preparation of - (10-phenothiazyl) propyl-phosphonic acid (described in scheme 2).
    [130] Steps (i) - (v) of Scheme 2 are described in relation to Scheme 1 of Example 1 (e).
    [131] XVa: - (10-phenothiazyl) propyl-phosphonate
    [132] β- (10-phenothiazyl) propyl chloride IX (5 g, 1.8 × 10 -2 M) was refluxed for 48 hours in 5 equivalents of triethyl phosphite. Unreacted triethylphosphite was removed by vacuum distillation to give the crude product XVa , which was used in the next step without further purification.
    [133] 1 H NMR (chloroform -d): δ1.17 - 1.22 (t , 6H, J = 7.1 Hz), δ1.79 - 1.92 (m, 2H), δ2.03 - 2.13 (m, 2H), δ3.92 - 4.14 (m, 6H), 6.84 - 7.17 (m, 8H, aromatic)
    [134] XVI: - (10-phenothiazyl) propylphosphono-trimethylsilyl ester
    [135] CHCl 3 (dry) cold solution of ⅩⅤa (0.15g, 4 × 10 -4 M) CHCl 3 ( dry) in the bromo-trimethylsilane was added (0.18g, 1.2 × 10 -3 M ) solution. The reaction mixture was stirred (0 < 0 > C, 1 hour) and then stirred at ambient temperature for 16 hours. The solvent was removed under reduced pressure to afford crude silyl ester XVI , which was used in the next step without further purification.
    [136] 1 H NMR (chloroform -d): δ.00 - 0.39 (s , 18H), δ1.75 - 1.90 (m, 2H), δ2.00 - 2.20 (m, 2H), δ3.84 (m, 2H) , [delta] 6.80 - 7.20 (m, 8H, aromatic)
    [137] XVII: - (10-phenothiazyl) propylphosphonic acid
    [138] The ⅩⅥ 1,4 - dioxane (1: 1) of H 2 O in the mixture for 2 hours and stirred at room temperature. The resulting precipitate was filtered and dried to obtain the crude product XVII .
    [139] 1 H NMR (methyl sulfoxide -d 6): δ1.55 - 1.67 ( m, 2H), δ1.78 - 1.84 (t, 2H), δ3.91 - 3.96 (t, 2H, J = 7.0 Hz), [delta] 6.8-7.3 (m, 8H, aromatic)
    [140]
    [141] The reagents and conditions used in the synthesis ( XVI ) of Scheme 2 are as follows:
    [142] (I) acrylonitrile, Triton B (40% aqueous solution), 0 占 폚; Reflux for 1 hour
    [143] (Ii) methanolic sodium hydroxide, refluxing for 15 hours;
    [144] (Iii) ethanol-toluene, concentrated H 2 SO 4 , refluxing for 12 hours;
    [145] (Iv) diethyl ether (dry), LiAlH 4 ;
    [146] (V) pyridine-chloroform (dry), phosphorus oxychloride, stirring at -15 [deg.] C for 2 h, stirring at RT for 1.5 h;
    [147] (Vi) triethyl phosphite, refluxing for 48 hours;
    [148] (Ⅶ) Dry chloroform, 0 ℃; Bromotrimethylsilane, dry chloroform, 0 ℃;
    [149] (Ⅷ) 1,4-dioxane / H 2 O (1: 1) and stirred at room temperature for 2 hours.
    [150] Example 4
    [151] Preparation of - (10-phenothiazyl) propionate phosphonic acid (described in scheme 3).
    [152] XXVI: - (10-phenothiazyl) propionitrile
    [153] Triton B (0.6 mL of 40% aqueous solution) was added to an aqueous solution of cold phenothiazine ( XXV , 50 g) in acrylonitrile (45 mL). After a while there was a violent reaction. The reaction mixture was heated with a steam bath for 2 hours and cooled. The resulting crude solid was crystallized from a mixture of hot ethanol and acetone 30:70 to give orange crystals XXVI .
    [154] XXVII: - (10-phenothiazyl) propionic acid
    [155] Compound XXVI (20 g) was refluxed in 450 mL of methanol sodium hydroxide (methanol: water, 350: 105 mL) for 15 hours. The crude product was poured into ice water and acidified by adding sulfuric acid (2 mol dm - 3). The crude product was crystallized from ethanol to give XXVII .
    [156] 1 H NMR (chloroform -d): δ2.26 - 2.67 (t , 2H, J = 7.9 Hz), δ4.04 - 4.09 (t, 2H, J = 7.9 Hz); [delta] 6.76 - 7.05 (m, 8H, aromatic)
    [157] XXVIII: - (10-phenothiazyl) propionic acid chloride
    [158] XXVII (1.0 g) was refluxed in 10 mL of oxazyl chloride for 3 hours. The oxalyl chloride was removed under reduced pressure to give the crude acid chloride XXVII , which was used in the next step without further purification.
    [159] 1 H NMR (chloroform -d): δ3.40 - 3.45 (t , 2H, J = 7.9 Hz), δ4.27 - 4.32 (t, 2H, J = 7.9 Hz); [delta] 6.87 - 7.25 (m, 8H, aromatic)
    [160] XXIX: - (10-phenothiazyl) propionate phosphate ester
    [161] XXVII (1.0 g) was dissolved in dry chloroform containing a small amount of pyridine. Diethylhydroxymethylphosphonate was added and the reaction mixture was stirred at room temperature overnight. The solvent was removed under reduced pressure to give the crude product XXIX , which was used without further purification in the next step.
    [162] 1 H NMR (chloroform -d): δ1.32 - 1.37 (t , 2H, J = 7.9 Hz), δ2.93 - 2.98 (t, 2H, J = 7.9 Hz); [delta] 4.12-4.28 (m, 6H, J = 7.9 Hz); [delta] 4.41-4.44 (d, 2H, J = 7.9 Hz); [delta] 6.89 - 7.22 (m, 8H, aromatic)
    [163] XXX: - (10-phenothiazyl) propionate Phosphono-trimethylsilyl ester
    [164] It was added trimethylsilane (0.18g, 1.2 × 10 -3 M ) solution - CHCl 3 (dry) CHCl 3 in a cold solution of ⅩⅩⅨ (1.0g) (dry) within bromo. The reaction mixture was stirred (0 < 0 > C, 1 hour) and then stirred at room temperature for 16 hours. The solvent was removed under reduced pressure to afford crude silyl ester XXX , which was used in the next step without further purification.
    [165] 1 H NMR (chloroform -d): δ0.00 (s, 18H ); delta 2.93-3.98 (m, 2H); [delta] 4.23-4.26 (m, 4H, J = 7.9 Hz); [delta] 7.11-7.19 (m, 8H, aromatic)
    [166] XXXI: - (10-phenothiazyl) propionate Phosphonic acid
    [167] XXX (1.0 g) were stirred in a mixture of 1,4-dioxane: H 2 O (1: 1) for 2 hours at room temperature. The resulting precipitate was filtered and dried to give the crude product XXXI .
    [168] 1 H NMR (methyl sulfoxide -d 6): δ2.93 - 2.98 ( m, 2H); [delta] 4.23-4.26 (m, 4H); [delta] 7.11-7.19 (m, 8H, aromatic)
    [169]
    [170] The reagents and conditions are as follows:
    [171] (I) Triton B, refluxed at < RTI ID = 0.0 > 0 C &
    [172] (Ⅱ) NaOH, CH 3 OH , reflux for 15 hours;
    [173] (Iii) oxazyl chloride, refluxing for 3 hours;
    [174] (Ⅳ) diethyl hydroxy methyl phosphonate, (dry) CHCl 3 / pyridine, stirred rt
    [175] (V) Bromotrimethylsilane, dry CHCl 3 , 0 C, stirred rt 16 h.
    [176] (Vi) 1,4-dioxane / H 2 O (1: 1), stirring rt 2 h.
    [177] Example 5
    [178] (1-ferrocenyl) imido-benzylmethylphosphonic acid (described in Scheme 4).
    [179] XXXII : (1- Ferrocenyl ) imido-benzyl diethyl phosphonate
    [180] Ferrocine aldehyde (2.5 g, 1.1 x 10 -2 M) was dissolved in toluene (80 mL). A catalytic amount of 4-amidobenzylphosphonate (2.6 g, 1.2 × 10 -2 M) and para-toluenesulfuric acid (0.13 g) was added and the reaction mixture was refluxed in a Dean-Stark setup for 3 hours. The solvent was concentrated under reduced pressure to give the crude product XXXII , which was all in the next step without further purification.
    [181] 1 H NMR (chloroform-d): d 1.25-1.3 (t, 6H, J = 7.0 Hz), 3.13-3.20 (d, 2H, J = 21 Hz); 4H, J = 7.0 Hz), 4.26-4.83 (m, 9H), d 7.12-7.33 (dd, 4H, aromatic), d 8.35
    [182] XXXIII : (1- Ferrocenyl ) imido-benzyl diethylphosphonate
    [183] Methanol (80mL) was added in hot (50 ℃) ⅩⅩⅩⅡ solution (5.39g, 1.2 × 10 -2 M ) solid NaBH 4 (0.5g, 1.2 × 10 -2 M) to. A vigorous reaction took place and the reaction mixture was refluxed for 3 hours. The reaction mixture was cooled to room temperature and stirred for 16 hours. The solvent was removed under reduced pressure and the crude product was obtained in chloroform (4 x 50 mL) and dried. The chloroform layer was washed with water and dried. The solvent was removed to give crude product, which was purified by column chromatography (100% CHCl 3) to obtain XXXIII .
    [184] 1 H NMR (chloroform -d): d 1.25 - 1.30 ( t, 6H, J = 7.0 Hz), d 3.04 - 3.11 (d, 2H, J = 21 Hz); 2H, aromatic) d 3.99 - 4.05 (q, 4H, J = 7.0 Hz), d 4.05-4.26 (m, 11H), d 6.62-6.65
    [185] XXXIV : (1- Ferrocenyl ) imido-benzyldiethyltrimethylsilyl ester
    [186] CHCl 3 (dry, 10mL) in cold ⅩⅩⅩⅢ (1.0g, 2 × 10 -3 M) in CHCl 3 (dry, 4mL) in a cold solution of bromo-trimethylsilane (2.0g, 1.3 × 10 -2 M ) solution of . The reaction mixture was stirred (0 < 0 > C, 1 hour) and then stirred at ambient temperature for 16 hours. The solvent was removed under reduced pressure to afford crude silyl ester XXXIV , which was used in the next step without further purification.
    [187] 1 H NMR (chloroform -d): d 0.00 (s, 18H), d 2.94 (d, 2H, J = 21 Hz), d 4.17 - 4.19 (m, 11H), d 6.79 - 6.85 (d, 2H, aromatic ), 7.09-7.20 (d, 2H, aromatic)
    [188] XXVI : (1- Ferrocenyl ) imido-benzylmethylphosphonic acid
    [189] The ⅩⅩⅩⅣ DMF / H 2 O: (1: 1) was stirred at room temperature for 4 hours. The precipitated crude product was filtered, washed with H 2 O and dried under vacuum to give XXXV .
    [190] 1 H NMR (methyl sulfoxide -d 6): d 2.71 - 2.78 (d, 2H, J = 21 Hz), d 3.93 - 4.26 (m, 11H), d 6.53 - 6.55 (d, 2H, J = 7.9 Hz ), 6.92-6.95 (d, 2H, J = 7.1 Hz)
    [191] 31 P NMR (methyl sulfoxide -d 6): d 24.4
    [192]
    [193] The reagents and conditions are as follows:
    [194] (I) toluene, para-toluenesulfuric acid, refluxing for 4 hours
    [195] (Ⅱ) sodium borohydride, CH 3 OH, reflux for 3 hours
    [196] (Ⅲ) bromo trimethylsilane, dry CHCl 3, 0 ℃, 0.5 hours; rt12 hours.
    [197] (Iv) Dimethylformamide / H 2 O (1: 1), rt 4 h.
    [198] Example 6
    [199] Preparation of - (10-phenoazyl) propionate phosphonic acid (described in Scheme 5).
    [200] XIX : β- (10- phenylazine ) propionitrile
    [201] Triton B (0.6 mL of 40% aqueous solution) was added to a cold phenolazine ( XVII , 50 g) solution in acrylonitrile (45 mL). After a while, a furious reaction occurred. The reaction mixture was heated with a steam bath for 2 hours and cooled. The resulting crude solid was crystallized from a 30:70 mixture of hot ethanol and acetone to give orange crystals IX .
    [202] XX: - (10-phenylazine) propionic acid
    [203] Compound XIX was refluxed in 450 mL of methanol, sodium hydroxide (methanol: water, 350: 105 mL) for 15 hours. The crude product was poured into ice water and acidified by addition of sulfuric acid (2 mol dm -3 ). The crude product was crystallized from ethanol to give XX .
    [204] 1 H NMR (chloroform -d): δ2.74 - 2.80 (t , 2H, J = 7,9 Hz); [delta] 3.90-3.96 (t, 2H, J = 7.9 Hz); [delta] 6.54 - 6.88 (m, 4H, aromatic)
    [205] XXI: - (10- phenylazine ) propionic acid chloride
    [206] XX (1.0 g) was refluxed in 10 mL of oxazyl chloride for 3 hours. The oxalyl chloride was removed under reduced pressure to give the crude chloride XXI , which was used in the next step without further purification.
    [207] 1 H NMR (chloroform -d): δ3.19 - 3.28 (t , 2H, J = 7,9 Hz); [delta] 3.90 - 3.99 (t, 2H, J = 7.9 Hz); [delta] 6.47-6.90 (m, 8H, aromatic)
    [208] XXII: - (10- phenylazine ) propionate phosphate ester
    [209] XXI (1.0 g) was dissolved in dry chloroform containing a small amount of pyridine. Diethylhydroxymethylphosphonate was added and the reaction mixture was stirred at room temperature overnight. The solvent was removed under reduced pressure to give the crude product XXII , which was used in the next step without further purification.
    [210] 1 H NMR (chloroform -d): δ1.35 - 1.42 (t , 6H, J = 6.9 Hz); [delta] 2.77-2.82 (d, 2H, J = 7.3 Hz); [delta] 3.91-3.96 (d, 2H, J = 7.6 Hz); [delta] 4.11-4.28 (m, 4H); [delta] 4.41-4.44 (d, 2H, J = 8.8 Hz); [delta] 6.55 - 6.87 (m, 8H, aromatic)
    [211] XXIII: - (10- phenylazine ) propionate Phosphono-trimethylsilyl ester
    [212] Was added trimethylsilane (0.18g, 1.2 × 10 -3 M ) - CHCl 3 ( dry) in CHCl 3 to cool ⅩⅩⅡ (1.0g) solution (dry) within bromo. The reaction mixture was stirred (0 < 0 > C, 1 hour) and then stirred at ambient temperature for 16 hours. The solvent was removed under reduced pressure to give crude silyl ester XXIII , which was used in the next step without further purification.
    [213] 1 H NMR (chloroform -d): δ0.0 (s, 18H ); [delta] 2.65-2.70 (t, 2H, J = 7.6 Hz); delta 3.80 - 3.86 (m, 2H); [delta] 4.25-4.36 (t, 2H, J = 10.0 Hz); [delta] 6.44 - 6.80 (m, 8H, aromatic)
    [214] XXIV: - (10- phenylazine ) propionate phosphonic acid
    [215] XXIII (0.1 g) was stirred in a mixture of 1,4-dioxane: H 2 O (1: 1) for 2 hours at room temperature. The resulting precipitate was filtered and dried to obtain the crude product XXIV .
    [216] 1 H NMR (methylsulfoxide-d 6 ): 隆 2.60 - 2.67 (m, 4H); [delta] 3.66 - 4.20 (t, 2H, J = 7.0 Hz); [delta] 6.49-6.86 (m, 8H, aromatic)
    [217] 31 P NMR (methylsulfoxide-d 6 ): 24.5
    [218]
    [219]
    [220] The reagents and conditions are as follows:
    [221] (I) Triton B, refluxed at < RTI ID = 0.0 > 0 C &
    [222] (Ⅱ) NaOH, CH 3 OH , reflux for 15 hours;
    [223] (Iii) oxazyl chloride, refluxing for 3 hours;
    [224] (Ⅳ) diethyl hydroxy methyl phosphonate, (dry) CHCl 3 / pyridine, stirred rt
    [225] (V) Bromotrimethylsilane, dry CHCl 3 , 0 C, stirred rt 16 h.
    [226] (Vi) 1,4-dioxane / H 2 O (1: 1), stirring rt 2 h.
    [227] Example 7
    [228] Stability experiment
    [229] Manufacture of nanostructured electrodes
    [230] All glasses were cleaned before use. Each plate was cleaned by hand using a detergent and then rinsed thoroughly with water. This was washed with acetone to remove all water and then the acetone was evaporated using hot air. Each membrane was placed using a docter-blading technique. The adhesive stencil was placed on each glass electrode while being arranged to leave a 5 mm perimeter. The glass surface was cleaned with iso-propanol and then reconstituted and placed. The sol precipitate was placed on one end of the glass, and the sol sediment was left on the opposite end of the glass using a glass rod (diameter: 7 mm). The negative electrode was a square TEC 15 glass plate of 50 mm x 50 mm in which a nanoporous nano-microcrystalline titanium dioxide (a film in Example 1 (a), except that the film was dried with hot air and sintered in air for 1 hour in a 40 mm x 40 mm square region ) Were coated with 0.5 centimeters left for the suture material. The anode was a square 50 mm × 50 mm square TEC 15 glass plate, except that the nanoporous nano-microcrystalline antimony doped with tin oxide in a 40 mm × 40 mm rectangular area at the center of the window was dried with hot air and sintered in air for 1 hour (Prepared as in Example 1 (a)) was covered with 1.5 centimeters left for the suture material.
    [231] Modification of nanostructured electrodes
    [232] Before reforming with the redox compound, the nanostructured cathode and anode were placed in an oven at 350 ° C to remove water vapor or organic material. The electrode was cooled to about 80 캜 before being put into the redox compound solution. All the cathodes composed of nanostructured TiO 2 working electrodes were charged with an aqueous solution (1 x 10 -2 mol) of biologic bis- (2-phosphonoethyl) -4,4'-bipyridinium dichloride in 0.1 M LiClO 4 dm -3 ) for 2 hours or more. After the derivatization reaction, each membrane was placed horizontally in an ethanol wash vessel for 1 minute. The washed, derivatized electrode was dried using hot air.
    [233] All the anode electrodes composed of tin oxide doped antimony were derivatized with a series of six redox promoters to obtain six sets of six windows summarized as follows.
    [234] Set A : No chemically adsorbed redox promoter on tin oxide doped antimony electrode.
    [235] Set B: Preparation of - (10-phenazoyl) propionate phosphonic acid solution (approximately 1 × 10 -3 M and 6 × 10 -3 M LiPF 6 in acetonitrile) prepared in Example 6 Six windows are immersed in this solution for 2 hours.
    [236] Set C : - (10-phenylazed) propoxyphosphonic acid solution (approximately 1 × 10 -3 M and 6 × 10 -3 M LiPF 6 in acetonitrile) prepared in Example 1 (e) And 6 windows are immersed in this solution for 2 hours.
    [237] Set D: A solution of - (10-phenothiazyl) propylphosphonic acid prepared in Example 3 (approximately 1 × 10 -3 M and 6 × 10 -3 M LiPF 6 in acetonitrile) was prepared Dip six windows into this solution for 2 hours.
    [238] Set E: Example 4 manufactured by a β- (10-phenothiazine nitrite) propionate phosphonic acid solution (approximately, chloroform / acetonitrile (4: 1) within about 1 × 10 -3 M and 6 × 10 - 3 M LiPF 6 ) was prepared and the six windows were immersed in this solution for 2 hours.
    [239] Set F: Example 5 prepared in (1-ferrocenyl) imido-phone benzyl methylphosphonate acid solution (approximately 1: 1 chloroform: dimethyl sulfoxide within about 1 × 10 -3 M and 6 × 10 -3 M LiPF 6 ) was prepared and the six windows were immersed in this solution for 2 hours.
    [240] After the derivatization reaction, each membrane was placed horizontally in a washing vessel of a solvent to modify it for 1 minute. The washed, derivatized electrode was dried using hot air. The window was stained immediately after coloring. The negative electrode and the positive electrode were arranged on the sandwich with the electrodes which were arranged to be shifted by 2-3 mm on the opposite sides to provide an area for external ohmic contact.
    [241] The switching time and stability of each of the devices (A-F) were tested as described in Example 2. The results are shown in Table 2-7. Optical absorption spectra were recorded using a Hewlett-Packard 8452A diode array spectrophotometer. The voltage-current characteristics were recorded using a Solartron SI 1287 constant voltage cascade. All recorded experiments were carried out at room temperature.
    [242]
    [243]
    [244]
    [245]
    [246]
    [247]
    [248] The results shown in the table can be explained as follows:
    [249] Permeability (%) in decolorized state - Percentage of light passing through a device that is colorless
    [250] Transmittance (%) in a colored state - Percentage of light passing through a device that is colored
    [251] Rectified current (SSC) - The value of current when equilibrium is reached
    [252] In general, the findings summarized for A-F in Tables 2-7 confirm that 40 mm x 40 mm EC windows assembled as described above are stable above 7000 electrochromic cycles in ambient laboratory conditions. In the achromatic state, the transmittance values are generally consistent throughout each experiment, indicating that much of the incident light passes through each device even after 7000 cycles. This indicates that there is indeed no optical resolution of the film. In the colored state, the transmittance value also generally agrees. The dynamic range between the transmittance in the colorless state and the transmittance in the colored state indicates a good performance as a cursor EC device. In the colored state, the SSC value is generally less than 25 micro amps cm -2 . This indicates that only a very small current is leaked. In each case, the SSC is in the state of 1 microamp-cm- 2 in the discolored state. This low power consumption accounts for the memory effect of the configured device. In addition, each device exhibits fast switching times in both colorless and colored states. 30 - 75 ms / cm 2 and the color-developing time range of 25 -. 50 ms / cm 2 bleaching time of this time is much faster than the switching time that can be obtained with the conventional apparatus had the switching time or more of 1 s / cm 2.
    [253] Compared to the conventional EC apparatus, the EC apparatus of the present invention has the following advantages:
    [254] 1. They switch quickly.
    [255] 2. They provide a dark color.
    [256] 3. Their color range is wider.
    [257] 4. They have low rectified current.
    权利要求:
    Claims (27)
    [1" claim-type="Currently amended] a conductive metal oxide nanoporous nano-microcrystalline film containing an electroactive compound which is a p-type or n-type redox stimulant or a p-type or n-type redox chromophore adsorbed on an electrode.
    [2" claim-type="Currently amended] The membrane of claim 1, wherein the conductive metal oxide is selected from the following.
    (a) SnO 2 doped with F, Cl, Sb, P, As or B;
    (b) ZnO doped with Al, In, Ga, B, F, Si, Ge, Ti, Zr or Hf;
    (c) In 2 O 3 doped with Sn;
    (d) CdO;
    (e) ZnSnO 3, Zn 2 In 2 O 5, In 4 Sn 3 O 12, GaInO 3 or MgIn ternary oxide, such as 2 O 4;
    (f) Sb and doped Fe 2 O 3 ;
    (g) TiO 2 / WO 3 or TiO 2 / MoO 3 systems; And
    (h) Fe 2 O 3 / Sb or SnO 2 / Sb system.
    [3" claim-type="Currently amended] The film according to claim 2, wherein the conductive metal oxide is SnO 2 doped with Sb.
    [4" claim-type="Currently amended] 4. The membrane according to any one of claims 1 to 3, wherein the electroactive compound is a p-type redox promoter or a p-type redox chromophore.
    [5" claim-type="Currently amended] 5. The membrane of claim 4, wherein the electroactive compound is selected from the following formula IV-VII.


    Wherein X in formula (V) is S or O and R 8 -R 10 are each independently selected from the following formulas:

    Wherein R 11 is C 1-10 alkyl and R 12 -R 15 are each independently hydrogen; C 1-10 alkyl; C 1-10 alkylene; Optionally substituted aryl; halogen; Nitro; Or an alcohol group, and n = 1 - 10.
    [6" claim-type="Currently amended] 6. The membrane of claim 5, wherein the electroactive compound is selected from:
    (1) - (10-phenothiazyl) propoxyphosphonic acid;
    (2) - (10-phenothiazyl) propyl-propionic acid;
    (3) - (10-phenylazine) propionate phosphonic acid;
    (4) - (10-phenothiazyl) propionate phosphonic acid; And
    (5) (1-Ferrocenyl) imido-benzylmethylphosphonic acid.
    [7" claim-type="Currently amended] The membrane of claim 3, wherein the electroactive compound is an n-type redox chromophile or an n-type redox chromophore, preferably an n-type redox chromophore selected from the following general formulas I-III.

    Wherein R 1 is selected from the following:


    R 2 is selected from C 1-10 alkyl, N-oxide, dimethylamino, acetonitrile, benzyl optionally mono- or di-substituted with nitro and phenyl;
    R 3 is C 1-10 alkyl and R 4 - R 7 is hydrogen; C 1-10 alkyl; C 1-10 alkylene; Aryl or substituted aryl; halogen; Nitro; Or an alcohol group;
    X is a charge balance ion which is preferably selected from chloride, bromide, iodide, BF 4 - , PF 6 - , and ClO 4 - , n = 1 - 10; Particularly, bis- (2-phosphonoethyl) -4,4'-bipyridinium dichloride.
    [8" claim-type="Currently amended] Use of a film according to any one of claims 1 to 7 for producing an electrode suitable for use in an electrochromic device.
    [9" claim-type="Currently amended] An electrode for use in an electrochromic device comprising a transparent or translucent substrate coated with electroconductive coating and containing a conductive nanostructured metal oxide film according to any one of claims 1 to 7.
    [10" claim-type="Currently amended] 11. The use of the electrode of claim 9 for the manufacture of an electrochromic device.
    [11" claim-type="Currently amended] An electrochromic device comprising at least one electrode according to claim 9.
    [12" claim-type="Currently amended] 12. The method of claim 11,
    (a) an n-type or p-type redox chromophore adsorbed on an n-type or p-type redox chromophore or an electrode, or an n-type redox chromophore or an accelerator adsorbed on an electrode if the metal oxide is a semi- A first electrode comprising a transparent or semitransparent substrate on which a nanostructured film containing a conductive or semiconductive metal oxide is electroconductive coated within the electrode;
    (b) if the first electrode contains an n-type redox chromophore or an accelerator, the first electrode contains a p-type or n-type redox chromophore adsorbed on the electrode, and the second electrode A second or opposite electrode comprising a transparent or semitransparent substrate on which a nanostructured film comprising a p-type redox promoter or a conductive metal oxide comprising a chromophore or vice versa is electroconductively coated within the electrode; And
    (c) the electrolyte between the electrodes.
    And an electrochromic device.
    [13" claim-type="Currently amended] 13. The method of claim 12 wherein the first electrode comprises a semiconductive metal oxide containing an n-type redox chromophore adsorbed to the electrode and the second electrode comprises a conductive metal oxide containing a p- And an electrochromic device.
    [14" claim-type="Currently amended] The method according to claim 12 or 13, wherein the semiconductive metal oxide is selected from the group consisting of titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, iron (Fe 2+ or Fe 3+ ) nickel or a perovskite, preferably a color developing electric apparatus is selected from TiO 2, WO 3, MoO 3 , ZnO or SnO 2.
    [15" claim-type="Currently amended] 15. The method according to any one of claims 12 to 14, wherein the first electrode is a negative electrode and the nanostructured film coated on the negative electrode is adsorbed on the negative electrode, wherein the nanostructured film comprises an n-type redox chromophore of formula I, II or III It contains TiO 2, which; Wherein the second electrode is an anode, and the nanostructured film coated on the anode is adsorbed on the anode, wherein the electrochromic device comprises SnO 2 : Sb containing the p-type redox promoter of the formula IV, V, VI or VII according to claim 5, .
    [16" claim-type="Currently amended] (a) an n-type or p-type redox chromophore adsorbed on an electrode, and a nano-type redox chromophore adsorbed on an electrode if the metal oxide is a semiconductive metal oxide, A first electrode comprising a transparent or semi-transparent substrate on which a structural film is electrically conductively coated within an electrode;
    (b) a second or opposite electrode comprising a transparent or semitransparent substrate on which a nanostructured film comprising a conducting metal oxide free of electroactive compounds adsorbed on the electrode is electrically coated within the electrode; And
    (c) the electrolyte between the electrodes.
    And an electrochromic device.
    [17" claim-type="Currently amended] The electrochromic device according to claim 16, comprising a semiconductive metal oxide containing an n-type redox chromophore according to claim 7, wherein the nanostructured film of the first electrode is adsorbed on the electrode.
    [18" claim-type="Currently amended] 18. The electricity generating device according to any one of claims 12 to 17, wherein the electrode is formed of glass coated with a glass or plastic material, preferably fluorine doped with tin oxide or indium tin oxide.
    [19" claim-type="Currently amended] 19. The electrochromic device according to any one of claims 12 to 18, wherein the electrodes are placed at an interval of 5 mm or more, preferably 50 占 퐉 to 5 mm.
    [20" claim-type="Currently amended] The electrochromic device according to any one of claims 12 to 19, wherein the electrolyte is liquid and preferably is a salt solution which is electrochemically inert in the solvent, in particular lithium perchlorate in -Butyrolactone.
    [21" claim-type="Currently amended] (a) providing a conductive, if appropriate, semiconductive nanostructured metal oxide film;
    (b) chemically adsorbing the resulting membrane, if appropriate, with a p- or n-type electroactive compound; And
    (c) applying a (deformed) film inside the first and second electrodes;
    (d) applying an electrolyte so as to lie on the electrode surface.
    The method of manufacturing an electrochromic device according to any one of claims 12 to 20,
    [22" claim-type="Currently amended] 22. The method of claim 21, wherein the conductive / semiconductive metal oxide film is exposed to an aqueous plasma stream prior to chemisorption of the electroactive compound.
    [23" claim-type="Currently amended] A use of the electrochromic device according to any one of claims 11 to 20 for an electrochromic window and a display.
    [24" claim-type="Currently amended] A compound of any one of formulas V, VI or VII according to claim 5.
    [25" claim-type="Currently amended] 24. The compound of claim 23, wherein formula V is:
    (1) - (10-phenothiazyl) propoxyphosphonic acid;
    (2) - (10-phenothiazyl) propyl-phosphonic acid;
    (3) - (10-phenothiazyl) propionate phosphonic acid; And
    (4) - (10-phenylazine) propionate Phosphonic acid.
    ≪ / RTI >
    [26" claim-type="Currently amended] 25. Compounds according to claim 24, wherein the compound of formula VII is (1-ferrocenyl) imido-benzylmethylphosphonic acid.
    [27" claim-type="Currently amended] Use of the compound of any one of claims 24 to 26 for the preparation of the membrane of any one of claims 1 to 7, or of the electrode of claim 9, or of the electrochromic device of any one of claims 11 to 20, Usage.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-10-11|Priority to IE990846
    1999-10-11|Priority to IES990846
    2000-10-11|Application filed by 유니버시티 칼리지 더블린
    2002-07-25|Publication of KR20020062286A
    2007-04-27|Application granted
    2007-04-27|Publication of KR100712006B1
    优先权:
    申请号 | 申请日 | 专利标题
    IE990846|1999-10-11|
    IES990846|1999-10-11|
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