WO2008083861A1 - Formulation électrochrome transparente à base organique, préparation d'un composant électrochrome transparent et utilisations de ce composant - Google Patents

Formulation électrochrome transparente à base organique, préparation d'un composant électrochrome transparent et utilisations de ce composant Download PDF

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Publication number
WO2008083861A1
WO2008083861A1 PCT/EP2007/059586 EP2007059586W WO2008083861A1 WO 2008083861 A1 WO2008083861 A1 WO 2008083861A1 EP 2007059586 W EP2007059586 W EP 2007059586W WO 2008083861 A1 WO2008083861 A1 WO 2008083861A1
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WO
WIPO (PCT)
Prior art keywords
formulation according
formulation
transparent
electrochromic
organic
Prior art date
Application number
PCT/EP2007/059586
Other languages
German (de)
English (en)
Inventor
Andreas Kanitz
Wolfgang Roth
Roland Wagner
Julia Wirsing
Original Assignee
Siemens Aktiengesellschaft
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Filing date
Publication date
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2008083861A1 publication Critical patent/WO2008083861A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

Definitions

  • Transparent organic based electrochromic formulation preparation of a transparent electrochromic device and uses therefor
  • the invention relates to an electrochromic formulation which is transparent in the visible spectral range.
  • Electrochromic devices that are transparent in the visible spectral range are suitable for specific applications such as windows and mirrors.
  • E lektrochrome transparent components previously known only inorganic based, ⁇ are too expensive very alswen dig in the manufacture and therefore nen for large Applikatio-.
  • Electrochromic displays based on organic materials to take ⁇ normally an active electrochromic layer, which is in the case of a display between the electrodes arranged perpendicular to each other.
  • Essential components of the active layer are a redox system and a pH-active dye.
  • the concent ⁇ rations collapse the redox partner is shifted from each other in the material.
  • protons and / or ions are released or bound in the material, which has an effect on the pH.
  • a voltage is applied to the material at ⁇ , then the displacement of the equilibrium of the redox partners of the two electrodes run in the opposite direction. This causes the pH at one electrode to rise while it sinks at the counterelectrode.
  • Via a pH dye the change in the pH value is then converted into a color change of the material and the application of the voltage is made visible.
  • a pasty formulation which represents the electrochromic system, is located between the electrodes.
  • the composition of this electrochromic system comprises as essential constituents a polymer as a solid electrolyte, a conductive salt, a redox system, TiO 2 as a white pigment, a solvent and ei ⁇ nen dye. This is usually a pH indicator.
  • TiO 2 as a white pigment are known, however, these find practically no application because of their low hiding power.
  • Another principle to realize electrochromic displays is to bring about the color change not by changing the pH in the display, but to use the already occurring redox processes to produce high-contrast color changes by the formation of reductive and / or oxidative states in suitable materials .
  • viologens and polythiophenes have become known as classes of materials. Examples in the literature for this are described in M.O.M. Edwards, Appl. Phys. Lett. 2005, 86 (7) and Helmut W. Heuer, Rolf Wehrmann, Stephan Kirchmeyer Adv. Funct. Mater. 2002, 89.
  • a white pigment Since a garstingli ⁇ cher color impression usually arises at the cathode or anode, a white pigment must be used to suppress the color impression of the, the viewer off, electrode. TiO 2 is widely used as a white pigment with high covering power . Cause a reduction of the content of white pigment, the layer thickness and / or the content of the electrochromically Akti ⁇ ven component to only unsatisfactory results to produce a transparent, that is translucent impression with backlighting.
  • Object of the present invention is therefore to provide an orgasmic ⁇ based electrochromic active formulation, with which a transparent electrochromic organic component can be produced.
  • the invention relates to an electrochromic formulation comprising the following materials: at least one chromophore and at least one associated redox partner in a matrix, inorganic and / or organic particles which are dispersed in the formulation and thus produce light scattering in the matrix. Moreover, the invention relates to a method for producing a transparent electrochromic organic component and finally the invention relates to the use of transparent electrochromic components in state displays, windows and / or mirrors.
  • Suitable inorganic particles that cause the light ⁇ scattering in the matrix are suitable, for example calcium carbonate, barium sulfate, talc, generally carbonates, bicarbonates, sulfates, hydrogen sulfates and phosphates, hydrogen phosphates of alkali and alkaline earth elements. Particularly suitable is calcium carbonate. Furthermore, oxides, hydroxides and / or mixtures thereof of the metals of the third and fourth main group can be used. As organic solvents or dispersing z. As polyethylene glycols particularly suitable. A particularly suitable system consists of silicon dioxide, preferably with particle sizes of 4 to 20 ⁇ m, dispersed in diethylene glycol.
  • the light scattering that occurs in the formulation can also be detected by the Tyndall effect.
  • the formulation is colloidal systems whose particle sizes are in the wavelength range of visible light. Depending on the particle size, the formulation may show high transparency in the visible spectral range or be opaque and opaque.
  • the formulation is arranged between two switchable electrode layers.
  • FIG. 1 shows the measurement setup for the so-called CVC measurement (current-voltage-contrast), in which a cyclic voltammetry of the overall electrochromic system is carried out and at the same time the discoloration and the transient current are recorded.
  • CVC measurement current-voltage-contrast
  • the transparent electrochromic cell 1 is irradiated with a light source 2, while the measured re ⁇ inflected light 3 with a photodetector. 4
  • the transparent EC display 1 is switched (circuit not shown for the sake of simplicity) that the Pho ⁇ todetektor 4 facing away from 5 darkened.
  • the light source 2 irradiates the transparent ⁇ EC cell 1 with festgeleg ⁇ ter intensity (white LED 30OmCd). If the EC cell 1 is not transparent, the color of the side 6 facing the photodetector does not change and the same intensity is reflected as in the non-connected state and the current of the photodetector 4 remains high.
  • the photodetector current necessarily sinks because the intensity of the reflected light decreases Absorption of part of the incident light in the discolored material).
  • the contrast is obtained by a darkening of the irradiated (and measured) surface in which the distance from the highest (initial state) at the lowest (Wired Mechanical state) Pho ⁇ todetektorstrom is determined.
  • the measurement is carried out for both sides (5,6), so it is once the photo ⁇ detector 4 facing side 6 and once the opposite side 5 examined.
  • the ratio of the measured contrasts for both cases provides as a first approximation a measurable statement for the transparency of the EC device.
  • examples of different transparent EC displays are presented.
  • Facing side 5 no discoloration (I max - I min ⁇ 0.1)
  • the formulation comprises a matrix in which a material for electrorochromic layers is based on a color change activated by redox reaction.
  • a material for electrorochromic layers is based on a color change activated by redox reaction.
  • the formulation can be described 10 2005 031634 and DE 10 2005 032081, also comprise a material such example ⁇ example in the documents DE.
  • Another embodiment of the invention is a matrix based on organic particles and consists in principle of a polymer in an only moderately good solvent. The transparent impression results from only incompletely dissolved polymer particles.
  • Particularly suitable is a mixture of polyvinylpyrrolidone, preferably with MW 1,300,000, or polyvinylcarbazole, preferably with MW 1,100,000 or polyethylene glycol, preferably with MW> 600,000 in diethylene glycol.
  • an electrochromic active component for example a polymeric 4,4'-bipyridinium salt (10 2005 032 316.2 DE, poly (dodecyl-4, 4 '- bipyridinium) -dibromid), mixed.
  • the materials are used anhydrous.
  • the use of anhydrous and / or free of water of crystallization materials because protic electrochemical reactions which disturb the redox chemistry of the EC cell and in particular attack the electrode materials are avoided.
  • the content of the coloring component the color depth can be adjusted by the content of the dispersed / colloidal particles, the transparency.
  • the color depth or the transparency can be adjusted by the layer thickness.
  • the electrochromic formulation with a layer thickness of less than 500 microns, more preferably less than 50 microns, transparent as a thin layer, in particular ⁇ sondere.
  • 6g SiO 2 at 4-20 ⁇ m are mixed with 0.6 g of a polymeric bipyridium salt (poly (dodecyl-4,4'-bipyridinium) -dibromide) and 0.23 g of a dimeric ferrocene derivative (1,2-diferrocenyl-1,2) dimethyl-ethylene) are intensively mixed together by means of a speed mixer.
  • a speed mixer To 10 g Diethylengklykol be given and mixed thoroughly this also means a speed mixer, a ⁇ .
  • a 50 ⁇ m thick layer is produced by means of the doctor blade technique on an ITO-coated film. This layer is transparent in transmitted light. If this layer is located between two ITO electrodes, a blue color is produced at the cathode when a voltage is applied, and a translucent color impression when illuminated.
  • Gradations in the light transmittance of a film produced from the Formu ⁇ -regulation can be achieved by the layer thickness of the film and / or by the size of the dispersed particles.
  • the invention relates to an electrochromic formulation which is transparent in the visible spectral range.
  • the transparency of the formulation is due to light scattering caused by particles in the formulation.
  • the transparency can be adjusted via the particle size and the layer thickness.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

L'invention concerne une formulation électrochrome transparente dans la plage visible du spectre. La transparence de la formulation est obtenue par une diffusion de la lumière provoquée par les particules présentes dans la formulation. La transparence peut être ajustée par l'intermédiaire de la taille des particules et de l'épaisseur de la couche.
PCT/EP2007/059586 2007-01-11 2007-09-12 Formulation électrochrome transparente à base organique, préparation d'un composant électrochrome transparent et utilisations de ce composant WO2008083861A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102007006017.5 2007-01-11
DE102007006017 2007-01-11
DE102007007102 2007-02-13
DE102007007102.9 2007-02-13

Publications (1)

Publication Number Publication Date
WO2008083861A1 true WO2008083861A1 (fr) 2008-07-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/059586 WO2008083861A1 (fr) 2007-01-11 2007-09-12 Formulation électrochrome transparente à base organique, préparation d'un composant électrochrome transparent et utilisations de ce composant

Country Status (1)

Country Link
WO (1) WO2008083861A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010037662A1 (fr) * 2008-09-30 2010-04-08 Siemens Aktiengesellschaft Composant organique électrochrome

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002075441A2 (fr) * 2001-03-19 2002-09-26 Dow Global Technologies Inc. Dispositif d'affichage electrochromique et compositions utilisees pour fabriquer de tels dispositifs
WO2004068231A1 (fr) * 2003-01-31 2004-08-12 Ntera Limited Afficheur electrochrome
WO2007006767A1 (fr) * 2005-07-11 2007-01-18 Siemens Aktiengesellschaft Structures de 4,4′-bipyridinium polymeres, formulations destinees a une couche electrochrome active et utilisation
WO2007107487A1 (fr) * 2006-03-23 2007-09-27 Siemens Aktiengesellschaft Composition pour un composant électrochrome, utilisation de ladite composition et composant électrochrome ainsi obtenu
WO2007107475A1 (fr) * 2006-03-23 2007-09-27 Siemens Aktiengesellschaft Produit intermédiaire pour la préparation d'une composition à activité électrochrome, composition à activité électrochrome obtenue et utilisations de ladite composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002075441A2 (fr) * 2001-03-19 2002-09-26 Dow Global Technologies Inc. Dispositif d'affichage electrochromique et compositions utilisees pour fabriquer de tels dispositifs
WO2004068231A1 (fr) * 2003-01-31 2004-08-12 Ntera Limited Afficheur electrochrome
WO2007006767A1 (fr) * 2005-07-11 2007-01-18 Siemens Aktiengesellschaft Structures de 4,4′-bipyridinium polymeres, formulations destinees a une couche electrochrome active et utilisation
WO2007107487A1 (fr) * 2006-03-23 2007-09-27 Siemens Aktiengesellschaft Composition pour un composant électrochrome, utilisation de ladite composition et composant électrochrome ainsi obtenu
WO2007107475A1 (fr) * 2006-03-23 2007-09-27 Siemens Aktiengesellschaft Produit intermédiaire pour la préparation d'une composition à activité électrochrome, composition à activité électrochrome obtenue et utilisations de ladite composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010037662A1 (fr) * 2008-09-30 2010-04-08 Siemens Aktiengesellschaft Composant organique électrochrome
US8373918B2 (en) 2008-09-30 2013-02-12 Siemens Aktiengesellschaft Electrochromic organic component

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