WO2006094052A2 - Electrolytes polymeres en gel - Google Patents

Electrolytes polymeres en gel Download PDF

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Publication number
WO2006094052A2
WO2006094052A2 PCT/US2006/007255 US2006007255W WO2006094052A2 WO 2006094052 A2 WO2006094052 A2 WO 2006094052A2 US 2006007255 W US2006007255 W US 2006007255W WO 2006094052 A2 WO2006094052 A2 WO 2006094052A2
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electrochromic
cell
layer
electrochromic cell
substrate
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PCT/US2006/007255
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English (en)
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WO2006094052A3 (fr
Inventor
Bijan Ramard
Gregory A. Sotzing
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Triton Systems, Inc.
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Publication of WO2006094052A3 publication Critical patent/WO2006094052A3/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/161—Gaskets; Spacers; Sealing of cells; Filling or closing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/1502—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect complementary cell
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect the electrolyte is made of polymers

Definitions

  • Electrochromism refers to the ability to change the optical properties of a material upon application of a potential.
  • the tunability of the optical properties of conjugated polymers as a function of potential makes them very useful electrochromic materials.
  • Some of the key advantages of conjugated polymers over inorganic electrochromic materials include wide range of color tunability, ease of processing, low operational voltages and extraordinary color retention.
  • cones and rods There are two kinds of light receptors in human eye: cones and rods.
  • the former is sensitive to even small radiations but cannot perceive the different colors and are used under low illuminations and the latter can yield perceptions of the different colors, but need more radiation to get activated and are predominantly used in well illuminated conditions.
  • the scotopic vision refers to situations wherein the cones are used under poorly illuminated situations and photopic vision is related to the use of rods under well-lit conditions. In each situation the eye is more sensitive to some wavelengths and less to others, so each wavelength has a relative weight in the overall spectrum perceived by the eye. The relative values for each wavelength have been standardized by the Commission Internationale de PEclairage (CIE).
  • CIE Commission Internationale de PEclairage
  • Embodiments of the current invention include electrochromic cells and devices that include electrochromic cells in which a UV curable solid state gel polymer electrolyte has been incorporated.
  • Electrochromic cells of the current invention include a first transparent substrate to which a first electrically conductive transparent electrode may be bonded.
  • a first electrochromic layer may be bonded to the first electrically conductive transparent electrode.
  • a second transparent substrate may be similarly coated with a second electrically conductive transparent electrode and a second electrochromic layer may then be bonded to the electrically conductive transparent electrode.
  • a transparent UV curable solid state crosslinking gel polymer electrolyte may be placed between the first and second substrate such that the gel is in contact with both the electrochromic layers and there is substantially no contact between the electrochromic layers.
  • Substrates maybe glass, plastic, ceramic or combinations of these, and include polycarbonate, polyphosphonate, polyethylene tetraphthalate or combinations thereof.
  • Embodiments of the present invention include electrochromic devices in which the first and second electrically conducting electrodes include, metal oxides, doped metal oxides, ITO, FTO, SnO 2 , ZnO, AZO, In 2 O 3 , and combinations of these, and may include one or more electrochromic conducting polymer.
  • the electrochromic conducting polymer is PEDOT or PEDOT/PSS.
  • Embodiments of the UV curable solid state crosslinking gel polymer of the present invention may be made up of one or more macromonomer, a plasticizer, a photoinitiator, and an electrolyte salt.
  • Embodiments of the gel polymer include macromonomers such as poly(ethyleneglycol)ethylether methacrylate (MA), poly(ethyleneglycol)diacrylate (DA) and combinations of these and may be vinyl macromonomers with poly(ethyleneglycol) side chains.
  • Photoinitiators for use in several embodiments of the gel polymer may be benzophenone, 2,2-dimethoxy-2-phenylacetophenone (DMPAP) 5 dimethoxyacetophenone, xanthone, thioxanthone, and combinations of these.
  • DMPAP 2,2-dimethoxy-2-phenylacetophenone
  • the electrolyte salt may be lithium salts, BF 4 " , ClO 4 " , CF 3 SO 3 " , (CF 3 SO 3 ) 2 N, and combinations of these.
  • the plasticizer may be alkylene carbonate, propylene carbonate, ethylene carbonate and combinations of these, and is about 1 % to 70 % by weight of the macromonomer, preferably about 5 to 50 %.
  • inert spacers are optionally dispersed within the gel polymer and act to keep the electrochromic layers from coming into contact with one another.
  • the first and second electrochromic layers may be deposited on the substrate using a variety of methods including, electrochemical deposition, spin coating, electrospinning, layer by layer self assembly, chemical casting composition, dip coating, ink jet printing or combinations of these formed on an electrode with a current density of greater than about 1 mC/cm 2 .
  • the first electrochromic layer is a cathodic electrochromic conducting polymer including PEDOT, PProDOT, PEDOP, PTT, PAEM-EDOT and combinations of these.
  • the second electrochromic device is an anodic electrochromic conducting polymer including poly(BEDOT-NMCz), PPro-NPrS, and derivatives and combinations of these.
  • the first and/or second elctrochromic layers may further include transition metal oxides, transition metal complexes, conducting polymers, viologens, polyaniline, polythiophene, WO 3 , Prussian Blue and combinations of these.
  • the electrochromic cells of the present invention may also include a barrier coating of nanoparticles in a resin that prevents crazing of the substrate during electrodeposition of the electrochromic layer and during polymerization of the gel polymer.
  • Embodiments of the invention also include a method for making electrochromic cells in which a gel polymer of one or more macromonomer, an electrolyte salt, and a plasticizer are photopolymerized between electrically conducting electrochromic layers.
  • the electrochromic layers may be bonded to transparent electrically conductive electrodes which may be bonded to transparent substrates.
  • the method of making an electrochromic device may be further described in some embodiments of the present invention which steps include; coating a first substrate with an electrically conductive transparent electrode, coating a second substrate with a second electrically conductive transparent electrode, coating the first coated substrate with a first electrochromic layer, coating the second coated substrates with a second electrochromic layer wherein the first electrochromic layer and the second electrochromic layer are different, covering the first coated substrate with the first electrochromic layer with a transparent, UV curable solid state cross linking gel polymer electrolyte mixture comprising one or more macromomoners, a plasticizer, a photoinitiator and an electrolyte salt, contacting the first coated substrate with the first electrochromic layer with the second coated substrate with the second electrochromic layer wherein the second electrochromic layer is in contact with the gel polymer electrolyte mixture and the first electrochromic layer is in contact with the gel polymer electrolyte mixture, and wherein there is substantially no contact between the first and second electrochromic layer, and sealing
  • the electrochromic cell is sealed by encapsulating it with a gel, and in some embodiments, adhesive copper tape covers the perimeter of the substrate, Sealing the cell substantially eliminates the intrusion of water, air, oxygen and other compounds into the polymeric gel.
  • FIG. 1. is an illustration of a potion of an electrochromic display device.
  • FIG. 2. shows chronocoulometric data obtained during polymerization of EDOT using metallic contact at one point (dotted line), one-side (dashed line), and whole perimeter (solid line) of the ITO glass.
  • FIG. 3. shows the relationship between charge density and polymerization time for a) PBENMCz and b) PEDOT.
  • FIG. 4. shows absorbance spectra of PEDOT and PBENMCz in the visible region.
  • FIG. 5 shows the relationship between charge density and contrast for PEDOT and PBENMCz.
  • FIG. 6. shows a dual polymer solid state device with an electrochromic area of ⁇ 30 cm 2 in the clear (65 %) and dark state (30 %).
  • FIG. 7. shows a photopically weighted transmittance spectrum of a solid state device in the clear and dark states.
  • FIG. 8. shows current (top) and change in % transmittance (bottom) for a dual polymer solid-state device measured as a function of the applied potential (referenced against PEDOT containing electrode).
  • FIG. 9. shows the switching of a solid state device between -1 and 1.4 V for about 90 k times.
  • FIG. 10 shows the percent transmittance change at 550 nm during potential stepping experiments for devices containing pure MA and DA as electrolytes.
  • FIG. 11 shows the percent transmittance change at 550 nm for different electrolytes a) MA b) DA during constant potential stepping between -1 and 1.4 V.
  • FIG. 12. shows cyclovoltammograms of a solid state electrochromic device
  • FIG 13. shows the optical tunability of a solid state device at different potentials and the ability of the device to hold the different optical states even after turning off the power supply (The transmittance was measured at 555 nm).
  • FIG. 14 shows the electrochromic response of an electrolyte containing electrochromic cell at room temperature and -3O 0 C at different biased voltages.
  • FIG. 15. shows the electrochromic response of ionic liquid containing electrochromic cell at room temperature and -3O 0 C at different biased voltages.
  • FIG. 16. shows temperature versus photopic transmission for an electrolyte containing electrochromic cell showing high and low points of transmission.
  • FIG. 17. shows the transmission at extreme temperatures of ionic liquid containing electrochromic cell.
  • FIG 18. shows the switching speed versus temperature of ionic liquid containing electrochromic cell.
  • FIG. 19 shows the switching speed versus temperature of electrolyte containing electrochromic cell.
  • Transmittance refers to the ratio of the radiant power transmitted through a material or device to the incident radiant power. Transmittance is usually expressed as a percent. For example, an electrochromic device with a 50% transmittance (at a specific wavelength) will absorb half of the light incident on it and allow half of it to pass through it. [0047] “Contrast ratio” is the ratio of the transmittance in the colored state and the transmittance in the bleached state (at a specific wavelength) for an electrochromic device.
  • the "switching speed" of an electrochromic device is the time that an electrochromic device needs to change the optical density from the fully bleached state to the fully colored state.
  • the temperature range over which an eletrochromic device can be operated properly is referred to as the "operating temperature”.
  • Electrochromism refers to the reversible change in optical properties that occurs when a material is oxidized (loss of electrons and charge balance by transport of negative counter ions) or reduced (gain of electrons and charge balance by transport of positive counter ions).
  • Polychromic materials may be used. Electrochromism includes devices that modulate radiation in the near infrared, thermal infrared, visible, and ultraviolet, and microwave regions. Electrochromic materials may be used with the photo-polymerized polymer electrolyte and may include but are not limited to transition metal oxides like WO 3 , Prussian blue, viologens, conducting polymers like polyanaline and polythiophenes, transition metal complexes, and other materials.
  • the present invention encompasses electrochromic devices with gel polymer electrolytes that are capable of undergoing an electrochromic color change.
  • FIG. 1 shows a general construction of a transmissive type electrochromic display device.
  • the display device has oppositely arranged front and back substrates 101, both may be transparent glasses, plastics, ceramics or combinations thereof.
  • a transparent conductive film like ITO is deposited on the inner surface of the front substrate 102, and, as a display working electrode, a first electrochromic layer is formed on the conductive film 103.
  • This display electrode is formed of a first type electrochromic material which assumes a characteristic color in an electrochemically oxidized or reduced state 103.
  • the inner surface of the back substrate is coated with a transparent conductive film 104, and, as a counter electrode, a second electrochromic layer is formed on the back or lower conductive film 105.
  • the counter electrode formed of a second type electrochromic material assumes a characteristic color in an electrochemically reduced or oxidized state, opposite to the state of the first electrochromic material 105.
  • the two substrates are held spaced from each other and may be separated by a sealing material that is applied peripherally of the substrates to surround the electrochromic layers and prevent intrusion of contaminants into the display and prevent material from leaving the cell.
  • the first electrochromic layer and the second electrochromic layer are separated by an electrolyte composition 106.
  • the substrate may be transparent, rigid or flexible, curved, lightweight, impact resistant or a combination of these.
  • suitable substrates include but are not limited to glass, ceramics and plastic, for example polycarbonate and polyphosphonate substrates may be used.
  • the substrate supports a transparent conductive inner layer and may serve as a barrier against permeation and diffusion of chemical contaminants into the electrochromic medium, for example oxygen, water or other contaminants.
  • Plastics in particular can be coated with layers that greatly reduce the permeation of contaminants into the cell.
  • the substrate may be coated with an elcetroconductive material, for example ITO, of sufficient thickness to allow electroconduction or may include layers of nonconducting transparent dielectrics such as, for example TiO 2 or SiO 2 coated on the plastic prior to coating with a transparent conductive material.
  • the substrate may be impregnated with small transparent conductive particles.
  • Electrically conductive transparent materials that may be used for the coating on the inside of the substrate can include but is not limited to metal oxides such as In 2 O 3 , SnO 2 , ITO, ZnO, or combination of these. These metal oxides can also be doped with traces of fluorides, antimony or aluminum to improve the conductivity. Other transparent conductive materials such as electrochromic conducting polymers, for example but not limited to PEDOT/PSS, or carbon nanotubes coatings may also be used.
  • a barrier polymer may be applied to the substrate to prevent diffusion and crazing of the substrate by solvents used in electropolymerization of the electrochromic layer as substrates that are used for electrochromic devices are generally susceptible to crazing in solvents like acetone, acetonitrile and other similar compounds.
  • the barrier coating may be an epoxy-based nanocomposite coating created from a solution of nanometer sized particles suspended in an epoxy-containing matrix that can be used to coat and protect substrate and acrylic surfaces, making them more rugged and reliable. For example, ITO coated polycarbonates substrates will be damaged by crazing as they are exposed to acetonitrile solvent used in the electropolymerization of conducting polymers during the fabrication of conducting polymer-based electrochromic devices.
  • anti-scratch coating maybe used as barrier coating for plastic substrates against acetonitrile.
  • Nanotuf® available from Triton Systems, Chelmsford, MA is a siloxane sol-get based nanocomposite coating created from a solution of nanometer sized particles suspended in an epoxy- containing matrix that may be used as a chemical barrier for polycarbonate substrates against solvent crazing or against acetonitrile crazing.
  • similar tests using a silicon based anti-scratch coating for commercial eyeware and goggles did not prevent crazing a plastic substrate when place in acetonitrile for electropolymerization reactions.
  • Suitable substrates may be dip coated with a siloxane sol-gel based nanocomposite coating as described above.
  • a transparent conductive coating such as but not limited to indium tin oxide may then be applied over the barrier coating. Immersion of the barrier coated substrates in acetonitrile, the media for electropolymerization of conducting polymers on the substrates, will precede the fabrication of dual conducting polymer-based electrochromic devices.
  • a cathodically electrochromic conducting polymer may be defined as a polymer that increases conductivity by donating positive charges.
  • Cathodically electrochromic conducting polymers on a first electrode that may be used with the solid state polymer gel electrolytes of the present invention include but are not limited to optionally substituted polypyrroles, polyanalines, polythiophenes and others.
  • the electrochromic conducting polymer for the first electrode are optionally substituted polythiophenes including but not limited to PEDOT or PEDOT prepared by electropolymerization.
  • Anodically electrochromic conducting polymers may be defined as polymers that increase conductivity by donating negative charges.
  • Anodically electrochromic conducting polymers for the second electrode may be the same or different than the electrochromic conducting solid state polymer of the first electrode and include but are not limited to optionally substituted polythiophene including [poly(bis-EDOT-N- methylcarbazole)] commonly referred to as PBEDOT-NMeCz or PBE ⁇ MCz.
  • dual polymer devices use for example PEDOT, PTT, PAEM- EDOT with poly(BEDOT- ⁇ MCz) and PAEBEDOT-NmeCz.
  • the electrochromic polymers disclosed herein may be prepared from monomers such as 3, 4-ethylenedioxythiophene (EDOT) and bis(3,4-ethylenedioxythiophene)-N-methyl carbazole (BENMCz).
  • Other electrochromic polymers that may be used include those disclosed in Avni, A. Argun, et. al. Multicolored Electrochromism in Polymers: Structures and Devices, Chem. Mater. Reviews (2004) 16(23), 4401-4412 and U.S. Patent No. 6,519,138 to Reynolds et al. the contents of which are hereby incorporated by reference in their entirety.
  • a potentiostat and an electrode may be used to electropolymerize PEDOT onto a transparent conductive substrates from an acetonitrile solution containing from about 20 mM to about 1 mM EDOT at about 1 to about 2.5 V preferably at about 1.3 V (vs Ag/ Ag+).
  • PBENMCz may be grown onto transparent conductive substrates from a solution containing about 0.5 to about 5.0 mM, preferably about 1 mM BENMCz with about 0.05 to about 1 M preferably about 0.1 M lithium salt at about 0.6 to about 1.2 V, preferably about 0.7 V (vs Ag/ Ag+).
  • FIG 2 shows chronocoulometric data obtained during polymerization of EDOT using metallic contact at one point (dotted line), one-side (dashed line), and whole perimeter (solid line) of the ITO glass.
  • the gel polymer electrolyte generally contains a salt with high ionic conductivity at room temperature and, preferably, is easy to handle while preparing the electrolyte.
  • Useful anions include but are not limited to BF 4 " , ClO 4 " , CF 3 SO 3 " , (CF 3 SO 3 ) 2 N) " , and the like or combinations of these.
  • the concentration of the electrolyte salt may be about 0.01 to about 20 wt % of the polymer, preferably from about 5 to about 20 wt %.
  • the salt used in the electrolyte is a lithium salt.
  • the salt is lithium trifluoromethanesulfonate (LITRIF). Ion transport evaluation of electrochromic devices may be performed using electrochemical quartz crystal microbalance (EQCM) techniques.
  • the gel electrolytes of the present invention may include a vinyl macromonomer with poly(ethylene glycol) side chains and may be prepared using the macromonomer, a photoinitiator and a plasticizer to compensate for the charge injected into or extracted from the conducting polymer.
  • vinyl macromonomers that may be used to form the gel electrolyte can include but are not limited to poly(ethyleneglycol)ethylether methacrylate (MA), poly(ethyleneglycol) diacrylate (DA).
  • MA poly(ethyleneglycol)ethylether methacrylate
  • DA poly(ethyleneglycol) diacrylate
  • the gel may be prepared using a photoinitiator.
  • Polymerization of the monolithic gel may be achieved using hydrogen abstracting photoinitators including, but not limited to, benzophenone, 2,2-dimethoxy-2-phenylacetophenone (DMPAP), dimethoxyacetophenone, xanthone, and thioxanthone.
  • the initiator may include 2,2-dimethoxy-2- ⁇ henyl-acetophenone (DMPAP).
  • Polymerization may also be thermally induced at about 4O 0 C to about 7O 0 C, preferablty about 5O 0 C using peroxide initiators such as benzyl peroxide (BPO) or azo bis isobutylnitrile (AIKN).
  • BPO benzyl peroxide
  • AIKN azo bis isobutylnitrile
  • Plasticizers may be added to the photo-polymerized gel-electrolyte to modify the mechanical properties, charge transport, and switching response of the cell.
  • These may be high boiling organic liquids and may include alkylene and alkylyne carbonates, such as but not limited to propylene and propylyne and their blends or other materials like dimethylformamide (DMF).
  • the amount of plasticizer added to the gel polymer can range from about 0 to about 50% by weight, or about 10 to about 30% by weight. Higher percentages of plasticizer may be used if the cell is suitably sealed.
  • the gel electrolyte solution may be poured onto the first conducting polymer electrode coated on a transparent substrate
  • polymer electrode coated on another transparent conductive substrate may be then placed over the first conducting polymer electrode with the conducting surfaces facing each other.
  • Inert spacers such as for example glass beads may be dispersed in the gel electrolyte to keep the two electrodes from contacting one another in the solid-state device.
  • the two electrodes may be pressed together to remove any trapped air bubbles and squeeze out excess gel electrolyte solution.
  • Polymerization of the macromonomer in the gel electrolyte may be carried out in at a suitable wavelength of light and temperature for a period of time that results in the polymerization or gel formation. For example, UV light from a lamp source can be used.
  • the device including two conductive substrates each having an electrochromic material electrode with a gel polymer electrolyte between them may be sealed together using polymer such as but not limited to a UV cross-linkable polymeric gel.
  • the device may be further treated by encapsulating it in a resin to reduce or eliminate loss of any plasticizer used or reduce or eliminate the intrusion of contaminants like moisture and or oxygen into the cell.
  • the quality of encapsulation may be tested by immersing the devices into a slightly acidified aqueous solution containing, for example, an Iron (III) thiocyanate complex. Poorly sealed devices are totally delaminated and the gel electrolyte may crack completely with uptake of the intensely colored dye. No change in the switching response (contrast and switching speed) was observed for well sealed devices even after subjecting the devices to vacuum at 75°C.
  • steps may be taken (i.e. the choice of electrode materials) to reduce a drop in potential along the surface and provide a more uniform deposition of electrochromic polymer films, thickness, with increasing distance from the applied potential contact point.
  • steps may be taken (i.e. the choice of electrode materials) to reduce a drop in potential along the surface and provide a more uniform deposition of electrochromic polymer films, thickness, with increasing distance from the applied potential contact point.
  • one way to provide a more uniform deposition is to cover the perimeter of the outer substrate plate with an adhesive copper tape. This leads to a lower gradient of the electric field all along the surface, leading to more uniform films.
  • the charge density on the electrode may also be used to modify the polymerization and deposition uniformity. An increase in the charge density (i.e., rate of polymer deposition) leads to thicker films.
  • Charge density can range from about 1 mC/cm 2 to about 50 mC/cm 2 .
  • the electrochemical cell for electropolymerization allows use of an adhesive copper contact which is advantageous since in traditional electrochemical cells, all but one side of the plate is immersed in the solution.
  • the electrode materials, cell configuration and current density are adjusted to where the relationship between the charge density and time of polymerization are approximately linear as shown in FIG 3 a and 3b, and visually confirmed that the thickness gradient all along the surface was minimized.
  • the optical characteristics of the working and counter electrode materials chosen for the electrochromic device may have complementary colors or approximately complementary colors in the charged or neutral states.
  • the optical characteristics of PEDOT and PBENMCz are complementary.
  • PEDOT is a cathodically coloring electrochromic conducting polymer that has been used in several electrochromic devices and goes from a transparent sky blue in its oxidized state to a deep indigo blue in the neutral state with a maximum absorbance centered at ⁇ 620 run.
  • PBENMCz goes from a pale
  • the anodically coloring electrochromic PBENMCZ has been shown to be a suitable complementary polymer of PEDOT. Spectrums of both polymers were taken in their reduced and oxidized forms, and they are shown in FIG. 4.
  • a series of electrochromic polymers prepared at various charge densities may be prepared.
  • the transmittance spectrum of the polymers prepared with the different charge densities in the charged and neutral state can be measured.
  • the contrast characteristics of PEDOT and PBENMCz may be obtained from polymer films prepared with increasing charge densities.
  • the transmittance spectrum of PEDOT in the neutral and oxidized forms may be recorded at constant potentials of -1.2 V and -0.15 V (vs Ag/ Ag+) respectively.
  • the neutral and oxidized form transmittance spectra of PBENMCz may be obtained at constant potentials of -0.7 V and 0.2 V (vs Ag/Ag+) respectively.
  • the absorption of the substrate and transparent conductive electrode and the electrolyte solution are preferably subtracted.
  • the photopic transmittance in the clear and dark states and the photopically weighted contrast i.e., the difference between the values in the clear and dark states
  • the relationships between contrast and charge density as related to the thickness of the film for each polymer can be plotted as illustrated in FIG. 5a and 5b.
  • an electrochromic display that includes electrochromic polymer electrodes has a stable, variable transmission, at least 85% photopic at twilight and at least 30% photopic at daylight with fast-switching elements of about 0.1 to about 0.25 sec.
  • the electrochromic display is a helmet mounted display (HMD's)
  • the electrochromic multi-layer, dual polymer devices with gel polymer electrolyte may use PEDOT, PTT, PAEM- EDOT with poly(BEDOT-NMCz) and PAEBEDOT-NMeCz on both flat and curved substrates.
  • the performance of fabricated electrochromic devices maybe evaluated in terms of switching time and transmission contrast at environmental chambers under different humidity (30% to 90% relative humidity) and temperature (between -30 ° and 80 0 C) conditions. These devices may be tested at reduced pressures.
  • a cycling voltage to operate the cell may be determined by cycling cells at different voltages and monitoring changes in the % T in the clear state after a number of cycles. Potential cycling or stepping can be used to identify the preferred device voltage for a desired operating life.
  • Other cell parameters that can be evaluated by potential cycling may include the rise time, switching time from dark to clear state, and fall time, switching time from clear to dark states of the solid-state devices.
  • FIG. 15 shows the electrochromic response of an ionic liquid containing electrochromic cell at room temperature and -3O 0 C at different biased voltages
  • FIG. 16 shows the electrochromic response of an electrolyte containing electrochromic cell at room temperature and -3O 0 C at different biased voltages.
  • the first electrochromic layer may be formed in a desired pattern such as a letter or image.
  • the second electrochromic layer that serves as the counter electrode is formed over almost the entire effective surface area of the underlying conductive film.
  • the first electrochromic layer patterns may be individually addressable and can be used to form pixels in a display.
  • the gel polymers described in the present invention contain ionic liquids.
  • Ionic liquids are organic salts with melting points under about 100°C, or lower than for example less than room temperature.
  • Examples of ionic liquids that may be used in the present invention include but are not limited to imidazolium, pyridinium, phosphonium or tetralkylammonium based compounds, for example, l-Ethyl-3-methylimidazolium tosylate, l-Butyl-3-methylimidazolium octyl sulfate; l-Butyl-3-methylimidazolium 2-(2- methoxyethoxy)ethyl sulfate; l-Ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide; 1 -Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; l-E
  • Ionic liquids allow effective ion transport even at low temperatures.
  • Conventional electrochromic cells have limited operational temperature range since at low temperatures electrolytes do not support ionic conduction in the cell, and at very low temperatures electrolytes may freeze.
  • the use of ionic liquids in gel polymer containing electrocliromic cells alleviates this problem creating an electrochromic cell with an operational temperature range from about -3O 0 C and 95 0 C.
  • the operating voltage range of electrochromic cells containing a gel polymer with an ionic liquid may be better than that of conventional electrolyte containing electrochromic cells.
  • the operating range of the device described in the present invention may be from about -1 to 1.4 volts. Increasing the voltage range may improve the contrast and a switching speed of the devices that utilize ionic liquids.
  • ionic liquids in electrochromic cells eliminates the need for plasticizers in the gel since ions in the ionic liquid may be capable of catalyzing polymerization.
  • the amount of ionic liquid in the gel polymer can range from about 10% to about 80% by weight, or from about 30% to about 60% by weight, hi one embodiment the ionic liquid used in the gel polymer is n-BMIMPF 6 .
  • Ion transport evaluation of electrochromic devices may be performed using electrochemical quartz crystal microbalance (EQCM) techniques.
  • compositions and devices described herein including a solid state gel electrolyte include improved safety for users, especially electrochromic display devices used in helmets, glasses and other devices located close to the eyes of the user.
  • Other examples of devices or applications for the use of elctrochromic devices including gel electrolytes include but are not limited to mirrors, optical shutters, windows, goggles, color changeable eyewear, automotive windows, aircraft windows, welding visors or other devices that can change optical or more generally electromagnetic transmission as a result of an applied potential.
  • Still further examples include readable displays.
  • Electrochromic devices may also be used in larger applications.
  • large area windows may be prepared that include two different conjugated polymers as working and counter electrode and a photo-polymerized gel including an electrolyte between them.
  • Conjugated polymers that can be used include those whose interaction with electromagnetic radiation can be reversibly changed by application of an external voltage to the polymer to cathodically or anodically charge the polymer.
  • These electrochromic polymers may be electrochemically grown or formed on large conductive transparent electrodes or other substrates coated with a transparent electrically conductive film.
  • visible light transparent conductive metal oxides like ITO coated glass and ITO coated poly(ethylene terephthalate) films can be coated with electropolymerized electrochromic polymers to form electrodes for the device.
  • electropolymerization is preferred for making the polymer electrodes, chemical polymerization may also be used.
  • This example illustrates an electrochromic display device as illustrated in FIG. 1 having electrochromic working and counter electrodes, and a UV curable polymer gel electrolyte.
  • the PEDOT electrochromic electrode was grown electrochemically onto 3" X 3" in ITO glass at 1.3 V (vs Ag/ Ag+) from an acetonitrile solution containing 20 mM EDOT, while the PBENMCz electrochromic electrode was grown onto 3" X 3" ITO coated PET from a 1 mM BENMCz solution with 0.1 M LITRIF at 0.7 V (vs Ag/Ag+). ITO glass and PET-ITO were used as substrates for the cell.
  • CHI 400 and CHI 660 A potentiostats were used for the electropolymerization of EDOT and BENMCz. These potentiostats were also used for the switching studies and other electrochemical characterizations of the solid state device. A UV lambda 900 spectrophotometer was used for the optical studies on the devices.
  • Electropolymerization of conjugated polymers could be performed in a cell designed for the electropolymerization on 3x3 inches plates but could be used for substrates of a variety of sizes.
  • PEDOT was grown in the oxidized transmissive sky-blue color form, was washed with acetonitrile and dried.
  • PBENMCz was reduced to the pale yellow neutral form at -1 V washed with acetonitrile and dried before constructing the device.
  • the gel electrolyte was composed of a vinyl macromonomers with poly(ethylene glycol) side chains (poly(ethyleneglycol)ethylether methacrylate (MA) and poly(ethyleneglycol) diacrylate (DA)), photoinitiator (2,2-dimethoxy- 2-phenyl-acetophenone (DMPAP)), plasticizer (propylene carbonate) and an electrolyte salt (Lithium trifluoromethanesulfonate (LITRIF)) to compensate for the charge injected into or extracted from the conducting polymer.
  • Several preparations of the gel electrolyte composition are shown in Table 1. Table 1. Different composition of gels
  • the device was then sealed using a polyurethane based UV curable resin to avoid loss of any plasticizer used or moisture affecting the gel electrolyte.
  • the quality of sealing was tested by immersing the devices into a slightly acidified aqueous solution containing an Iron (III) thiocyanate complex.
  • This example illustrates characterization of devices and modification of electropolyrnerization variables to change device performance.
  • One way to obtain the maximum contrast in a dual polymer configuration was to make a series of different charge density films, ranging from 3xlO "3 to 2.8x10 '2 C/cm 2 for PEDOT, and from IxIO "3 to 5.5xlO "3 C/cm 2 for PBENMCz, combining each film of one polymer with the whole group of the other, and then measured the contrast attained for each dual polymer configuration. It was determined from this set of experiments that improved contrast was shown with PEDOT and PBENMCz grown to charge densities of 1.5x10 "2 mC/cm and 1.9x10 " mC/cm respectively. [0096] The above contrast values are for the conjugated polymers alone.
  • the cell itself without the conjugated polymer maybe made from materials that are transmissive throughout the electromagnetic region of interest, for example the infrared or the visible region.
  • the devices in this example (ITO glass and PET-ITO), were found to have about 80 % transmissivity throughout the visible region without the electrochromic materials. Furthermore, since transmittance and absorbance have a logarithmic relation, the maximum contrast achievable with the device is different. The contrast with different permutations and combinations was found to be about ⁇ 30 % with the clear state transmittance at about 65 % for polymerization charge densities of 9x10 "3 mC/cm 2 and 2.IxIO "3 mC/cm 2 for EDOT and BENMCz.
  • FIG. 6 shows the solid state device with a clear state and dark state photopic transmittance of 65 and 35 %.
  • the photopically weighted transmittance spectrum of a device in the clear and dark state is shown in FIG. 7.
  • a high clear state transmittance provides for good visibility with maximum contrast.
  • FIG. 8 shows the cyclic voltammogram of a dual polymer solid-state device obtained at a scan rate of 100 mV/sec and the corresponding change in % transmittance.
  • -1 V i.e., clear state
  • PEDOT is in the conductive oxidized state
  • PBENMCz is in the insulating neutral state and at a potential of 2.0 V when the device is dark it is vice-versa.
  • An asymmetry or hysteresis between the anodic and cathodic branches is observed in redox processes of conducting polymers. Energetic differences between doping and dedoping processes, may be related to asymmetric structural changes in the electrode materials necessary to complete them.
  • This example illustrates how device performance can be related to electrode polymer composition, electrolyte composition, and preparation.
  • This example illustrates device characterization.
  • the switching response from colored to bleached states is show in FIG. 10 for different macromonomers.
  • the switching times from colored to bleached states for mixture of different macromonomers and different amounts of plasticizer are shown in FIG. lla and 1 Ib.
  • FIG. 13 shows the optical tunability and memory retention of a solid state device at different potentials.
  • the solid state device initially held at -1.1 V was pulsed to various potentials viz. -1 to 1.4 V and the power was turned off after 10 seconds of pulse width while the transmittance data at 555 nm was gathered for another two minutes. Except for a small increase (about 1-2%) in the % T just after turning off the potential the device was holding the different colored states for a long time to the order of several hours (although not shown here for clarity).
  • the drop in % T between -1 and -0.2 V is very gradual and then there is a faster drop in the % T values till about 0.8 V and again rate of change in % T with potential decreases till 1.4 V.
  • This comparative example shows a comparison of an ionic liquid and an electrolyte in the gel polymer. Ionic liquid Based Devices.
  • Oxidized PEDOT in the clear state was electrochemically grown on
  • ITO-Glass at 1.3 V (vs AgAAg + , 0.46 V vs NHE) to a charge density of 12.9 mC/cm 2 .
  • PBEDOT-NMCz was grown on ITO-PET at 0.7 V (vs AgAAg + ) to a charge density of 2.73 mC/cm 2 and further reduced at -1 V to obtained the clear state.
  • the electrolyte comprised of 6g of n-BMIMPF 6 , 4g PEGDA, lO.Omg 2,2-dimethoxy-2-acetophenone (photoinitiator) and 5 mg glass beads (50-100 micron) was sandwiched between the two electrodes and cured for 20 min using a UV lamp (365nm, 5.8 mW/cm 2 ) with the PET-ITO containing PBEDOT-NMCz on top. The device was sealed with UVS-91, UV curable polymers for 3 min using UV-lamp at the above mentioned conditions. LiTRIF electrolyte gel based devices.
  • Control Oxidized PEDOT in the clear state was electrochemically grown on ITO-Glass at 1.3 V (vs AgZAg + , 0.46 V vs NHE) to a charge density of 11.6 mC/cm 2 .
  • PBEDOT-NMCz was grown on ITO-PET at 0.7 V (vs AgZAg + ) to a charge density of ' 2.77 mC/cm 2 and further reduced at -1 V to obtained the clear state.
  • the electrolyte comprised of 3g of propylene carbonate, 7g PEGMA, Ig lithium trifluoromethane sulfonate, 20.0mg 2,2-dimethoxy-2-acetophenone (photoinitiator) and 5 mg glass beads (50-100 micron) was sandwiched between the two electrodes and cured for 20 min using a UV lamp (365nm, 5.8 mW/cm 2 ) with the PET-ITO containing PBEDOT-NMCz on top. The device was sealed with UVS-91, UV curable polymers for 3 min using a UV-lamp at the above mentioned conditions. Comparison
  • FIG. 16, 17, 18 and 19 show that the rate of switching speed is faster across a wide temperature range in electrochromic cells using ionic liquids than in LiTRTF devices.

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Abstract

L'invention concerne une cellule électrochromique pouvant comprendre une première électrode transparente électriquement conductrice collée à une première électrode électrochromique obtenue par électrochimie, sur la surface de l'électrode; une seconde électrode transparente électriquement conductrice collée à une seconde électrode électrochromique obtenue par électrochimie, sur la surface de la seconde électrode; et un électrolyte polymère en gel transparent formé à partir d'un ou de plusieurs macromonomères mélangés à un agent plastifiant et à un sel d'électrolyte. L'électrolyte polymère en gel est en contact avec à la fois la première et la seconde électrodes électrochromiques, lesquelles électrodes électrochromiques sont séparées l'une de l'autre.
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WO2008034532A1 (fr) * 2006-09-20 2008-03-27 Bayer Materialscience Ag Assemblage électrochrome
US7518778B2 (en) 2006-09-20 2009-04-14 Bayer Materialscience Ag Electrochromic arrangement
WO2015018948A1 (fr) * 2013-08-07 2015-02-12 Intercomet, S.L. Cellule électrochrome flexible
WO2016163966A1 (fr) * 2015-04-07 2016-10-13 Grafentek Yazilim Arge San. Tic. Ltd. Sti. Cellule électrochromique et procédé de production de cellule électrochromique
US10824040B2 (en) 2018-07-16 2020-11-03 Polyceed Inc. Insulated glass unit utilizing electrochromic elements
US20200225549A1 (en) * 2018-07-16 2020-07-16 Polyceed Inc. Perimeter Sealant for an Electrochromic Device
WO2020018410A1 (fr) * 2018-07-16 2020-01-23 Polyceed Inc. Compositions polymères destinées à être utilisées dans une transmission variable et dispositifs électrochimiques
US10948795B2 (en) * 2018-07-16 2021-03-16 Polyceed, Inc. Perimeter sealant for an electrochromic device
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US11287716B2 (en) 2018-07-16 2022-03-29 Polyceed Inc. Methods of making ion-conductive polymer films for electrochromic devices
CN113614629A (zh) * 2019-03-29 2021-11-05 金泰克斯公司 具有电致变色凝胶层的电光子组合件和组合件
CN112255854A (zh) * 2020-11-06 2021-01-22 广西大学 一种锌离子驱动二氧化钛电致变色器件及其制备方法
CN112255854B (zh) * 2020-11-06 2022-12-23 广西大学 一种锌离子驱动二氧化钛电致变色器件及其制备方法

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