WO2015130227A1 - Electrochromic active multilayer film, device comprising the same, and method of fabricating the device - Google Patents
Electrochromic active multilayer film, device comprising the same, and method of fabricating the device Download PDFInfo
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- WO2015130227A1 WO2015130227A1 PCT/SG2015/000055 SG2015000055W WO2015130227A1 WO 2015130227 A1 WO2015130227 A1 WO 2015130227A1 SG 2015000055 W SG2015000055 W SG 2015000055W WO 2015130227 A1 WO2015130227 A1 WO 2015130227A1
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- Prior art keywords
- poly
- multilayer film
- electrochromic
- complexes
- electrochromic active
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- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- G02F1/155—Electrodes
-
- 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
- FIG. 6 is a Nyquist plot of [PEO-PAA/PAA-PEO] 8 and [PEO-PAA] 48 .
- the electrochromic active material comprises or consists of conducting polymers.
- the electrochromic active material may be selected from the group consisting of polyaniline (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxythiophene):polystyrene sulfonate, poly(3,4- ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)/ poly(ethylenimine), polypyrrole, polypyridyl complexes, polymers containing viologen moieties, poly(butanyl viologen), derivatives thereof, and combinations thereof.
- PANI polyaniline
- PEDOT poly(3,4-ethylenedioxythiophene)
- PDOT poly(3,4-ethylenedioxythiophene):polystyrene sulfonate
- PDOT:PSS poly(ethylenimine)
- polypyrrole polypyr
- Suitable polyanions may include anionic polyelectrolytes which have high solubility in aqueous solution or which have low steric hindrance.
- examples of polyanions include, but are not limited to, poly(styrene sulfonic acid), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), sulfated polyvinyl alcohol), poly(vinylsulfonic acid), poly(acrylic acid-co-maleic acid), poly(styrene sulfonic acid-co- maleic acid), poly(ethylene-co-acrylic acid), poly(phosphoric acid), poly(silicic acid), hectonte, bentonite, alginic acid, pectic acid, xanthan, gum arabic, dextran sulfate, earboxy methyl dextran, earboxy methyl cellulose, cellulose sulfate, cellulose xanthogenate, starch sulf
- Example 2 Approach to fabricating electrochromic device (Embodiment 2)
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
An electrochromic active multilayer film obtainable by layer-by-layer (LbL) assembly is provided. The film comprises alternating layers of an electrochromic active material and a polyelectrolyte complex. An electrochromic device and a method of fabricating an electrochromic device are also provided.
Description
ELECTROCHROMIC ACTIVE MULTILAYER FILM, DEVICE COMPRISING THE SAME, AND METHOD OF FABRICATING THE DEVICE
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of priority of US provisional application No. 61/944,701 filed on 26 February 2014, the content of which is incorporated herein by reference in its entirety for all purposes.
TECHNICAL FIELD
[0002] Various embodiments relate to an electrochromic active multilayer film, an electrochromic device comprising the multilayer film, and method of fabricating an electrochromic device.
BACKGROUND
[0003] Electrochromism may be described as a persistent, reversible color and/or opacity change of a material upon application of a voltage across the material. Generally, electrochromic active materials demonstrate a memory effect, in that reversal of color and/or opacity does not take place until an oppositely polarized potential is applied. In other words, a burst of electricity is required to change color and/or opacity of the electrochromic active materials, biit once the change has been effected, electricity is not required to maintain the change.
[0004] Typically, energy required to drive electrochromic active materials is very low, involving an operating potential of only a few volts, and are able to provide suitable contrasts with charge transfer of only several millicoulombs of electrical charge per square centimeter of display area. This makes electrochromic devices very attractive due to their low energy consumption.
[0005] Although this phenomenon has been extensively studied for more than 40 years, there are only a very limited number of commercial electrochromic products due to problems faced by state of the art fabrication processes and electrochromic active materials.
[0006] For example, state of the art processes to fabricate electrochromic products have low production rates, due to the need for tens or even hundreds of layers to be packed together as a film in order to get sufficient optical modulation. In addition, the electrochromic
active materials exhibit poor stability, which may manifest in the form of severe peeling after several color and/or opacity changing cycles, thereby limiting their practicality in commercial applications.
[0007] In view of the above, there exists a need for an improved electrochromic device and methods of fabricating the electrochromic device that overcome or at least alleviate one or more of the above mentioned problems.
SUMMARY
[0008] In a first aspect, an electrochromic active multilayer film obtainable by layer-by- layer (LbL) assembly is provided. The film comprises alternating layers of an electrochromic active material and a polyelectrolyte complex.
[0009] In a second aspect, an electrochromic device comprising one or more electrochromic active multilayer films according to the first aspect is provided.
[0010] In a third aspect, an electrochromic device is provided. The electrochromic device comprises
a) a first electrode and a second electrode;
b) a first electrochromic active multilayer film and a second electrochromic active multilayer film, each according to an electrochromic active multilayer film according to the first aspect; and
c) an electrolyte;
wherein the first electrochromic active multilayer film and the second electrochromic active multilayer film are deposited on the first electrode and the second electrode, respectively, and then arranged facing each other with the electrolyte being sandwiched between the first electrochromic active multilayer film and the second electrochromic active multilayer film.
[001 1] In a fourth aspect, a method of fabricating an electrochromic device using layer- by-layer assembly is provided. The method comprises
a) depositing a first electrochromic active multilayer film and a second electrochromic active multilayer film, each according to an electrochromic active multilayer film according to the first aspect, on a first electrode and a second electrode respectively;
b) depositing an electrolyte on at least one of the first electrochromic active multilayer film or the second electrochromic active multilayer film; and
c) arranging the first electrochromic active multilayer film and the second electrochromic active multilayer film facing each other with the electrolyte being sandwiched between the first electrochromic active multilayer film and the second electrochromic active multilayer film.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The invention will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and the accompanying drawings, in which:
[0013] FIG. 1 is a schematic illustration of structure of polymeric complexes layer-by- layer (LbL) electrolyte film according to embodiments, where polymeric complexes LbL film is sandwiched between two [PAA/PEI]n protecting layers.
[0014] FIG. 2 is a schematic illustration of the process of all-solid electrochromic devices fabricated by LbL assembly according to embodiments. In the embodiment shown, an electrolyte (LbL Electrolyte Layer) is sandwiched between a first electrochromic active multilayer film (LbL EC layer 1) and a second electrochromic active multilayer film (LbL EC layer 2), and the film layers are arranged between two conductive electrodes.
[0015] FIG. 3 shows (A) and (B) top-view scanning electron microscopy (SEM) images of the [PANI/PAA-PEI]20 film; (C) cross-section image of the [PANI/PAA]20 film; and (D) shows cross-section image of the [PANI/PAA-PEI]20 film. Scale bar denotes (A): 1 μπι; (B) to (D): 100 nm.
[0016] FIG. 4 depicts electrochromic behaviors of [PANI/PAA]30 and [PANI/PAA-PEI]30 films, where a graph of transmittance (%) versus time (s) for switching time calculation at 630 nm is shown.
[Q017] FIG. 5 shows (A) UV-Vis transmittance spectra (in 1M LiC104 in propylene carbonate (PC)) of colored and bleached device-(PSS) and device-(PSS-PEI); (B) transmittance response of device-(PSS) (dash) and device-(PSS-PEI) (solid) at 630 nm. The potential was switched between -1.5 V to +1.5 V for device-(PSS) and -0.5 V to +1.5 V for device-(PSS-PEI).
[0018] FIG. 6 is a Nyquist plot of [PEO-PAA/PAA-PEO] 8 and [PEO-PAA]48.
DETAILED DESCRIPTION
[0019] As disclosed herein, polyelectrolyte complexes and polymeric complexes are used instead of pure polymers to fabricate electrochromic active and electrolyte multilayer films. Advantageously, both polyelectrolyte complexes and polymeric complexes possess larger dimensions compared to pure polymers, thereby providing faster rate of film growth during fabrication. In particular, polyelectrolyte complexes usually exhibit special structures of hydrophobic cores and hydrophilic shells in aqueous solution, and the special spatial structures and large amount of charges that the polyelectrolyte complexes carry may cause relatively large repulsion between complexes to facilitate formation of porous structures. The porous structure of the polyelectrolyte complexes translates into improvements in electrolyte diffusion and proton transfer. Porous structures may also be formed by polymeric complexes due to presence of multi-components in the polymeric complexes, and interaction of specific steric configuration between the components.
[0020] By carefully designing the components and other deposition conditions, such as pH and ion strength, polyelectrolyte complexes are able to act as carriers and traps of protons during redox process of electrochromic active materials, to facilitate reaction and to improve electrochromic properties of resulting devices.
[0021] The electrochromic active multilayer films containing the polyelectrolyte complex may be prepared using layer-by-layer (LbL) assembly. A solid state electrochromic device with all components in the solid state, including polymeric complexes as electrolyte, may also be fabricated using the layer-by-layer (LbL) assembly. Advantageously, the LbL technique allows tailoring of film structures to achieve desired properties, as well as to integrate multi-functions into the device.
[0022] Compared to conventional films, the electrochromic active multilayer films disclosed herein demonstrate rapid growth and porous structures, which facilitate diffusion of electrolyte in electrochromic applications. Protons earned by the polyelectrolyte complexes also promote redox reaction of electrochromic active materials such as polyaniline (PANI) which are placed in ion transfer relationship with the complexes, leading to improvements in electrochromic properties.
[0023] With the above in mind, various embodiments refer in a first aspect to an electrochromic active multilayer film obtainable by layer-by-layer (LbL) assembly. The film
comprises alternating layers of an electrochromic active material and a polyelectrolyte complex.
[0024] As used herein, the term "electrochromic active material" refers to a material that is able to reversibly change its optical properties, such as color and/or opacity, due to insertion or extraction of charge carriers such as ions in the material. An electrochromic active material may, for example, change from a colored state to being transparent upon application of a voltage across the material. By varying the voltage applied across the electrochromic active material, a complete set of tones may be obtained. The electrochromic active material may additionally or alternatively change between an opaque state, a translucent state, and a transparent state.
[0025] Examples of electrochromic active materials include transition metal oxides, molecular dyes, and conducting polymers.
[0026] Transition metal oxides that function as electrochromic active materials may include an oxide of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and alloys thereof. Specific examples of transition metal oxides that may function as electrochromic active materials include tungsten oxide (W03), nickel oxide (NiO), vanadium oxide (V205), titanium oxide (Ti02), molybdenum oxide (Mo03), and combinations thereof.
[0027] Molecular dyes that may function as electrochromic active materials include viologens such as 1 ,1 '-diethyl-4,4' dipyridilium dichloride (also known as ethyl viologen or EV), and 1 , 1 '-dimethyl-4,4' dipyridilium dichloride (also known as methyl viologen, or MV).
[0028] Examples of conducting polymers include, but are not limited to, polyacetylene, polyaniline, polythiophene, polypyrrole, polyarylene, polyphenylene, poly(bisthiophenephenylene), poly-methylpyrrole, conjugated ladder polymer, poly(arylene vinylene), poly(arylene ethynylene), polymers containing viologen moieties, such as poly(butanyl viologen), derivatives thereof, copolymers thereof, and combinations thereof.
[0029] In various embodiments, the electrochromic active material comprises or consists of conducting polymers. For example, the electrochromic active material may be selected from the group consisting of polyaniline (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxythiophene):polystyrene sulfonate, poly(3,4- ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)/ poly(ethylenimine),
polypyrrole, polypyridyl complexes, polymers containing viologen moieties, poly(butanyl viologen), derivatives thereof, and combinations thereof.
[0030] As used herein, "derivative" refers to a chemically modified version of a chemical compound that is structurally similar to a parent compound, and which is actually or theoretically derivable from that parent compound. Derivatization may involve substitution of one or more moieties within the molecule, such as a change in functional group. A derivative may or may not have the same chemical and/or physical properties of the parent compound. For example, the derivative may be more hydrophilic, or it may have altered reactivity as compared to the parent compound.
[0031] One specific example of a derivative of poly(3,4-ethylenedioxythiophene) is poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), which is a commercially available electrochromic active material, and which is also a polyelectrolyte complex. PEDOT has in its oxidized form, good hole conductivity, but is as such unstable in water. By using PSS as a charge-balancing dopant during polymerization, a water-soluble polyelectrolyte complex PEDOT:PSS possessing good film forming properties, high conductivity (about 10 S/cm), high visible light transmissivity, and excellent stability may be obtained. As PEDOT:PSS may be negatively charged, it may be formed along with a polycation such as PEI, which is positively charged to render a stable PEDOT:PSS/PEI electrochromic active material layer.
[0032] In various embodiments, the electrochromic active material comprises or consists of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate. In some embodiments, the electrochromic active material may comprise or consist of poly(3,4- ethylenedioxythiophene):polystyrene sulfonate/ poly(ethylenimine).
[0033] In specific embodiments, the electrochromic active material comprises or consists of polyaniline.
[0034] The electrochromic active multilayer film disclosed herein comprises alternating layers of an electrochromic active material and a polyelectrolyte complex. The term "alternating" as used herein refers to a configuration of the layers of electrochromic active material and the layers of polyelectrolyte complex, whereby a layer of electrochromic active material is positioned next to a layer of polyelectrolyte complex and stacked in an alternating sequence.
[0035] As mentioned above, color and/or opacity changes in the electrochromic active material may be effected by ions entering and leaving the electrochromic active material. By arranging the layer of polyelectrolyte complex directly on the layer of electrochromic active material, the polyelectrolyte complex is in contact with the electrochromic active material, and may furthermore be in an ion-transfer relationship with the electrochromic active material. The polyelectrolyte complex may thus function as an ion-conductor to complete an electrical circuit. By allowing ions to migrate between two outer electrodes sandwiching the electrochromic active multilayer film, the polyelectrolyte complex may carry the electrical current needed for color and/or opacity changes in the electrochromic active material.
[0036] As used herein, the term "polyelectrolyte complex" refers to a polymer-polymer complex composed of macromolecules carrying charges of opposite sign. The macromolecules carrying charges of opposite sign may otherwise be termed as "polyelectrolyte", and may include polymers that have either cationic or anionic groups chemically bonded to a polymer chain. Polymers having cationic groups chemically bonded to a polymer chain may have a positive net charge, and may be termed as a polycation, while polymers having anionic groups chemically bonded to a polymer chain may have a negative net charge, and may be termed as a polyanion.
[0037] In various embodiments, the polyelectrolyte complex comprises at least one polymer having a negative net charge and at least one polymer having a positive net charge. Preferably, the polyelectrolyte complex is non-electrochromically active.
[0038] Depending on the type and ratio of polymers contained in the polyelectrolyte complex, for example, the polyelectrolyte complex may be neutral or may possess a charge, such as a positive charge or a negative charge.
[0039] For example, the polyelectrolyte complex may be neutral when the negative and positive charges on the polymers in the polyelectrolyte complex cancel out, such that the overall charge on the polyelectrolyte complex is zero.
[0040] The polyelectrolyte complex may alternatively contain an electric charge. For example, when charge of macromolecules having a negative charge outweighs charge of macromolecules having a positive charge, overall charge on the polyelectrolyte complex may be negative. Conversely, when the polyelectrolyte complex may be positively charged when charge of polymers having a positive charge outweighs charge of polymers having a negative charge.
[0041] Due to the opposite charges, the macromolecules may be bound together by electrostatic interactions. The complex is usually formed by the electrostatic interaction of oppositely charged polyelectrolytes, such as an anionic polyelectrolyte or polyanion, and a cationic polyelectrolyte or polycation.
[0042] Suitable polyanions may include anionic polyelectrolytes which have high solubility in aqueous solution or which have low steric hindrance. Examples of polyanions include, but are not limited to, poly(styrene sulfonic acid), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), sulfated polyvinyl alcohol), poly(vinylsulfonic acid), poly(acrylic acid-co-maleic acid), poly(styrene sulfonic acid-co- maleic acid), poly(ethylene-co-acrylic acid), poly(phosphoric acid), poly(silicic acid), hectonte, bentonite, alginic acid, pectic acid, xanthan, gum arabic, dextran sulfate, earboxy methyl dextran, earboxy methyl cellulose, cellulose sulfate, cellulose xanthogenate, starch sulfate, starch phosphate, lignosulfonate, polygalacturonic acid, polyglucuronic acid, polyguluronic acid, polymannuronic acid, chondroitin sulfate, heparin, heparan sulfate, hyaluronic acid, dennatan sulfate, keratan sulfate; poly-(L)-glutamic acid, poly-(L)-aspartic acid, acidic gelatins (A-gelatins); starch, amylose, amylopectin, cellulose, guar, guar gum, pullulan, dextran, chitin or chitosan derivatives having the following functional groups: carboxymethyl, carboxyethyl, carboxypropyl, 2-carboxyvinyl, 2-hydroxy-3-carboxypropyl, 1,3-dicarboxyisopropyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 2-hydroxy-3-sulfopropyl, 2,2-disulfoethyl, 2-carboxy-2-sulfoethyl, maleate, succinate, phthalate, glutarate, aromatic and aliphatic dicarboxylates, xanthogenate, sulfate, phosphate, 2,3-dicarboxy, N,N-di(phosphatomethyl)aminoethyl, N-alkyl-N-phosphatomethylaminoethyl, and combinations thereof.
[0043] Examples of polycations include, but are not limited to, poly(aniline); poly(pyrrole); poly(alkylenimines); . poly-(4-vinylpyridine); poly(vinylamine); poly(2- vinylpyridine), poly(2-methyl-5-vinylpyridine), poly'(4-vinyl-N-Cl-C18-alkylpyridinium salt), poly(2-vinyl-N-Cl-C18-alkylpyridinium salt), polyallylamine, aminoacetylated polyvinyl alcohol; poly-(L)-lysine, poly-(L)-arginine, poly(ornithine), basic gelatins (B- gelatins), chitin or chitosan derivatives having the following functional groups: 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-diisopropylaminoethyl, 2- dibutylaminoethyl, 3-diethylamino-2-hydroxypropyl, N-ethyl-N-methylaminoethyl, 2- diethylhexylaminoethyl, 2-hydroxy-2-diethylaminoethyl, 2-hydroxy-3-
trimethylammonionopropyl, 2-hydroxy-3-triethylammonionopropyl, 3- trimethylammonionopropyl, 2-hydroxy-3-pyridiniumpropyl, S,S-dialkylthioniumalkyl, and combinations thereof.
[0044] The polyelectrolyte complex may be formed by mixing a polycation and a polyanion, such as that listed above. Various unit molar ratios of the polycation and polyanion, which may be calculated based on total number of polymer units, may be used. The ratio may be varied to render the polyelectrolyte complex charge neutral, or to confer a net charge on the polyelectrolyte complex.
[0045] In embodiments where the polyelectrolyte complex is negatively charged, for example, ratio of polycation to polyanion may be controlled such that dominant charge on the polyelectrolyte complex is negative. Conversely, in embodiments wherein the polyelectrolyte complex is positively charged, ratio of polycation to polyanion may be controlled such that dominant charge on the polyelectrolyte complex is positive.
[0046] Unit molar ratio of polycation to polyanion may be varied to obtain polyelectrolyte complex of a specific charge to suit specific applications. The unit molar ratio used may in turn depend on properties of the polyanion and/or polycation, as well as the specific polyanion-polycation combination. By controlling molar ratio of polycations to polyanions, for example, the polyelectrolyte complex may be transformed from being a negatively charged polyelectrolyte complex to a positively charged polyelectrolyte complex, vice versa.
[0047] In various embodiments, the polyelectrolyte complex comprises a first polymer and a second polymer. The first polymer may be one or more polymers made up of ethylenically unsaturated monomers having a negatively charged functional group, while the second polymer may possess opposite charges or be oppositely charged to the first polymer. For example, the first polymer may be selected from the group consisting of poly(sodium-4- styrenesulfonate), poly(acrylic acid), copolymers thereof, and combinations thereof; while the second polymer may be selected from the group consisting of poly(diallydimethylammonium chloride), poly(ethylenimine), poly(allylamine hydrochloride), copolymers thereof, and combinations thereof.
[0048] For example, the polyelectrolyte complex may be strong polyelectrolytes pairs, such as poly(sodium-4-styrenesulfonate)-poly(diallydimethylammonium chloride) (PSS- PDDA) complexes; a strong polyelectrolyte-weak polyelectrolyte pair, such as PSS-PEI complexes or PSS-poly(allylamine hydrochloride) (PAH) complexes; or weak polyelectrolyte
pairs, such as poly(acrylic acid) (PAA)-PEI complexes, which are able to act as dual proton carrier systems.
[0049] In various embodiments, the polyelectrolyte complex is selected from the group consisting of poly(sodium-4-styrenesulfonate)-poly(diallydimethylammonium chloride) (PSS-PDDA) complex, polystyrene sulfonate-poly(ethylerieimine) such as poly(sodium-4- styrenesulfonate)-poly(ethylenimine) (PSS-PEI) complex, poly(sodium-4-styrenesulfonate)- poly(allylamine hydrochloride) (PSS-PAH) complex, poly(acrylic acid)-poly(ethylenimine) (PAA-PEI) complex, poly(methacrylic acid)-polyallylamine hydrochloride (PMAA-PAH) complex, and combinations thereof. The polyelectrolyte complexes listed may be negatively charged complexes.
[0050] In some embodiments, the polyelectrolyte complex is a negatively charged polyelectrolyte complex.
[0051] One or more polyelectrolyte complexes may be used. The one or more polyelectrolyte complexes may be comprised in different layers, each layer containing the same or different polyelectrolyte complexes.
[0052] In embodiments where the polyelectrolyte complex carries a charge, the alternating layers of an electrochromic active material and a polyelectrolyte complex may be held in place by electrostatic interaction between the electrocliromic active material and the polyelectrolyte complex. Presence of the charges on the electrochromic active material and the polyelectrolyte complex also facilitates formation of the electrocliromic active multilayer film during layer-by-layer (LbL) assembly.
[0053] For example, electrochromic active material polyaniline may be a polycation carrying positive charges. By using a polyelectrolyte complex carrying negative charges, the positively charged electrochromic active material may be attracted to the negatively charged polyelectrolyte complex by electrostatic interaction to result in a stable electrochromic active multilayer film. Conversely, in embodiments wherein the electrochromic active material comprises polyanions carrying negative charges, polyelectrolyte complexes carrying positive charges may be used.
[0054] In some embodiments, the electrochromic active multilayer film comprises alternating layers of polyaniline as the electrochromic active material, and polystyrene sulfonate-poly(ethyleneimine) as the polyelectrolyte complex.
[0055] Number of layers in the electrochromic active multilayer film is not particularly limited, and may be tailored according to intended properties of the electrochromic device. For example, number of layers in the electrochromic active multilayer film may be in the range of about 2 to about 100, such as about 2 to about 80, about 2 to about 60, about 2 to about 40, about 2 to about 20, about 20 to about 100, about 50 to about 100, about 80 to about 100, about 20 to about 80, about 30 to about 60, about 25 to about 75, about 40 to about 70, or about 20 to about 50. h specific embodiments, the electrochromic active multilayer film comprises about 20 to 80 layers.
[0056] As mentioned above, spatial structures and large amount of charges that the polyelectrolyte complexes carry may cause relatively large repulsion between complexes to facilitate formation of porous structures. In various embodiments, at least a portion of the electrochromic active multilayer film is porous. The porous structure may facilitate diffusion of electrolyte in electrochromic applications, thereby improving electrochromic properties.
[0057] Various embodiments refer in a second aspect to an electrochromic device comprising one or more electrochromic active multilayer film according to the first aspect, and in a further aspect to an electrochromic device comprising a) a first electrode and a second electrode; b) a first electrochromic active multilayer film and a second electrochromic active multilayer film; and c) an electrolyte. The first electrochromic active multilayer film and the second electrochromic active multilayer film are deposited on the first electrode and the second electrode, respectively, and may each be independently an electrochromic active multilayer film according to the first aspect. The first electrochromic active multilayer film and the second electrochromic active multilayer film are then arranged facing each other with the electrolyte being sandwiched between the first electrochromic active multilayer film and the second electrochromic active multilayer film.
[0058] The term "electrochromic device" as used herein refers to a device containing a material or compound which changes color and/or opacity upon application of an electric potential.
[0059] Examples of suitable electrochromic active material and polyelectrolyte complex have already been discussed above.
[0060] The first electrode and the second electrode may independently be an electrically conductive material. In various embodiments, the first electrode and the second electrode are independently a transparent electrically conductive material. As used herein, the term
"transparent" generally refers to a material allowing light to pass through without substantial portions being absorbed. Accordingly, a transparent electrically conductive material may be optically clear, and may have a visible light transmission in the range of 80 % to almost 100 %.
[0061] Examples of transparent material that may be used include glass, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polyimide, polydimethylsiloxane, and combinations thereof. In embodiments where the transparent material is not electrically conductive, it may be coated with an electrically conductive material such as indium tin oxide (ITO) to render it electrically conductive.
[0062] The term "electrolyte" refers to an ionic conductor which may be in a solid state, including in a gel form. The electrolyte may comprise a lithium salt. Examples of lithium salts that may be used include, but are not limited to, lithium perchlorate (LiC104), lithium chloride, lithium nitrate, lithium bromide, lithium fluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate (LiPF6), and combinations thereof. In specific embodiments, the electrolyte comprises lithium perchlorate (LiC104).
[0063] In various embodiments, the electrolyte comprises a polymer matrix. For example, the polymer matrix may comprise or consist of a polymer multilayer film comprising layers made of polymeric complexes. Similar to that of conventional liquid electrolyte, the polymeric complex may serve as a matrix for lithium salts for ion conducting purposes. Advantageously, use of a solid electrolyte such as a polymeric complex disclosed herein simplifies the manufacturing process, as a sealing process to seal the electrolyte between the two substrates, such as that used for liquid electrolyte, is not required. As in the case for the electrochromic active multilayer film, the polymer multilayer film comprising layers of polymeric complexes may be prepared by layer-by-layer (LbL) assembly. Coil structures and large dimensions of polymeric complexes compared to pure polymers provide loosely packed structures, which may result in low ionic cross-link density in the films as well as faster rate of film growth during fabrication.
[0064] The term "polymeric complex" or "polymer-polymer complex" as used herein refers to the association of two or more macromolecules due to favorable interactions between the macromolecules. For example, the polymeric complexes may be formed based on hydrogen bonding interaction, such as between poly(ethylene oxide) and poly(acrylic acid).
[0065] In some embodiments, the polymeric complexes are selected from the group consisting of poly(N-vinylpyrrolidone)-poly(methacrylic acid) (PVPON-PMAA) complexes, poly(acrylic acid)-poly(ethylene oxide) (PAA-PEO) complexes, PAA-PVPON complexes, PMAA-PEO complexes, polyvinyl alcohol (PVA)-PVPON complexes, PVA-PEO complexes, polydopamine (PDA)-PVPON complexes, PDA-PEO complexes, PAA-polyacrylamide (PAAM) complexes, PVA-PAAM complexes, PAA-poly(N-isopropyl acrylamide) complexes, poly(N-vinylcaprolactam)-PMAA complexes, and combinations thereof.
[0066] The polymer multilayer film may comprise alternating layers of poly(N- vinylpyrrolidone)-poly(methacrylic acid) (PVPON-PMAA) complexes and poly(acrylic acid)-poly( ethylene oxide) (PAA-PEO) complexes.
[0067] In some embodiments, the polymer multilayer film comprises alternating layers of poly(acrylic acid)-poly(ethylene oxide) (PAA-PEO) complexes and poly( ethylene oxide)- poly(acrylic acid) (PEO-PAA) complexes. The term "PAA-PEO" as used herein indicates that PAA is present in a greater amount than PEO, while the term "PEO-PAA" indicates that PEO is present in a greater amount than PAA. In PEO-PAA complexes, where PEO forms the dominating component, the complexes may function as hydrogen bond donors such as during LbL assembly or self-assembly. On the other hand, in PAA-PEO complexes, where PAA forms the dominating component, the complexes may function as hydrogen bond acceptors during LbL assembly. By alternately depositing layers of poly(acrylic acid)- poly(ethylene oxide) (PAA-PEO) complexes and poly(ethylene oxide)-poly(acrylic acid) (PEO-PAA) complexes, a stable solid polymer electrolyte layer may be obtained.
[0068] In various embodiments, unit molar ratio of PAA to PEO in the PAA-PEO complex is about 1 1 :3, while unit molar ratio of PEO to PAA in the PEO-PAA complex is about 49:1.
[0069] As mentioned above, use of polymeric complexes may translate into formation of porous structures. In various embodiments, one or more polymer layers, such as PAA and/or PEI, may be deposited to function as protecting layers to provide continuous and smooth interfaces, and/or to prevent other materials from diffusing into the polymeric complexes layer during electrochromic device fabrication. In this regard, polyelectrolyte complexes may not be suitable for use to form the protecting layers as they may not provide continuous and smooth interfaces, particularly, when compared to morphology of layers formed from polymers. In specific embodiments, the protecting layers comprises or consists of alternating
layers of PAA and PEI, which may be formed using layer-by-layer assembly. An example of such a structure is shown in FIG. 1.
[0070] In a fourth aspect, a method of fabricating an electrochromic device using layer- by-layer assembly is provided. The method comprises a) depositing a first electrochromic active multilayer film and a second electrochromic active multilayer film, each according to an electrochromic active multilayer film according to the first aspect, on a first electrode and a second electrode respectively; b) depositing an electrolyte on at least one of the first electrochromic active multilayer film or the second electrochromic active multilayer film; and c) arranging the first electrochromic active multilayer film and the second electrochromic active multilayer film facing each other with the electrolyte being sandwiched between the first electrochromic active multilayer film and the second electrochromic active multilayer film.
[0071] Examples of suitable electrochromic active material, polyelectrolyte complex, electrolyte and electrode have already been discussed above.
[0072] Depositing the first electrochromic active multilayer film or the second electrochromic active multilayer film on the respective electrode may include a) depositing a first layer comprising an electrochromic active material on the respective electrode; b) depositing a second layer comprising a polyelectrolyte complex on the first layer; and c) optionally repeating steps a) and b) for one and more additional cycles.
[0073] In various embodiments, each of steps a) and b) independently comprises contacting the deposited layer with water prior to a subsequent step. This may be carried out to remove any loosely bound material prior to deposition of a further layer.
[0074] Advantageously, LbL deposition technique is one of the most effective synthesis tools to fabricate highly-ordered nanoscale structures or patterns with extended functionalities, especially suitable for large area deposition. It is able to easily incorporate homo- or hetero-phase compounds into a single film through non-covalent interaction.
[0075] In various embodiments disclosed herein, layer-by-layer assembly may be carried out by submersing an electrode into a first liquid solution comprising an electrochromic active material. Prior to this, the electrode may be subjected to a pre-treatment, for example, using oxygen plasma or UV-light irradiation, to prepare and/or to clean the electrode.
[0076] The electrochromic active material may be adsorbed on a surface of the electrode until a first layer comprising or consisting of the electrochromic active material is deposited
on the electrode. The electrode may then removed from the first liquid solution, and exposed to one or more rinse baths containing water to remove any physically entangled or loosely bound electrochromic active material.
[0077] Following the rinse baths, the electrode may be exposed to a second liquid solution comprising a polyelectrolyte complex. The polyelectrolyte complex may be adsorbed on the first layer, until a second layer comprising or consisting of the polyelectrolyte complex is deposited on the first layer, where the polyelectrolyte complex may be in direct contact with the electrochromic active material.
[0078] The electrode may then be removed from the second liquid solution, and be exposed to one or more rinse baths containing water to remove any physically entangled or loosely bound polyelectrolyte complex.
[0079] The above process steps may be repeated one or multiple times to form a stack of or multiple alternating layers of electrochromic active material and polyelectrolyte complex on the respective electrode. As mentioned above, number of layers in the electrochromic active multilayer film is not particularly limited, and may be tailored according to intended properties of the electrochromic device.
[0080] In various embodiments, depositing a first layer comprising an electrochromic active material on the respective electrode and depositing a second layer comprising a polyelectrolyte complex on the first layer is carried out for 1 to 50 cycles. For example, a first layer comprising an electrochromic active material on the respective electrode and depositing a second layer comprising a polyelectrolyte complex on the first layer may be earned out for 1 cycle, 2 cycles, 3 cycles, 10 cycles, 20 cycles, 30 cycles, or 50 cycles. In so doing, the electrochromic active multilayer film may contain 2 to 100 layers, preferably 2 to 80 layers.
[0081] An electrolyte is deposited on at least one of the first electrochromic active multilayer film or the second electrochromic active multilayer film.
[0082] In various embodiments, the electrolyte comprises a polymer matrix, where the polymer may comprise or consist of a polymer multilayer film comprising layers made of polymeric complexes. Examples of suitable polymeric complexes have already been mentioned above.
[0083] Depositing an electrolyte on at least one of the first electrochromic active multilayer film or the second electrochromic active multilayer film may comprise a) depositing a first layer. comprising a first polymeric complex on the respective electrode; b)
depositing a second layer comprising a second polymeric complex on the first layer; and c) optionally repeating steps a) and b) for one and more additional cycles.
[0084] In various embodiments, depositing a first layer comprising a first polymeric complex on the respective electrode and depositing a second layer comprising a second polymeric complex on the first layer is carried out for 1 to 50 cycles. For example, depositing a first layer comprising a first polymeric complex on the respective electrode and depositing a second layer comprising a second polymeric complex on the first layer may be carried out for 1 cycle, 2 cycles, 3 cycles, 10 cycles, 20 cycles, 30 cycles, or 50 cycles. In so doing, the electrolyte may contain 2 to 100 layers of polymeric complexes.
[0085] The electrochromic active multilayer film and electrochromic device disclosed herein may be used in displays, smart windows, mirrors such as automatic anti-glazing mirror, switching devices, large-area information panels, electronic papers (e-papers), and chameleon materials. By applying an electric field with polarization to the electrocliromic active material, color of the one or more layers of electrochromic active material may be varied.
[0086] Hereinafter, the present invention will be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, lengths and sizes of layers and regions may be exaggerated for clarity.
[0087] As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
[0088] The invention illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed
herein. Thus, for example, the terms "comprising", "including", "containing", etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the inventions embodied therein herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention.
[0089] The invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
[0090] Other embodiments are within the following claims and non- limiting examples. In addition, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.
EXPERIMENTAL SECTION
[0091] Various embodiments relate to use of polyelectrolyte complexes and polymeric complexes instead of pure polymers to deposit LbL films for electrochromic applications, in an effort to fabricate fast growing films for electrochromic applications, as well as to improve the diffusion of electrolyte and protons transfer by taking advantages of specific steric configuration and multi-components of complexes. The LbL technique was also extended to propose an all-solid state electrochromic device with all the components, including electrolyte layer and electrocliromic active layers, fabricated by LbL deposition. To the inventors' best knowledge, this is the first time polyelectrolyte complexes are used to deposit LbL films for electrochromic study.
[0092] Example 1; Approach to fabricating electrochromic device (Embodiment 1)
[0093] In various embodiments, electrochromic active multilayer films of PANI and polyelectrolyte complexes were deposited layer-by-layer, and paired with two electrodes to form an electrochromic device. Fabrication procedures included:
[0094] 1) Formation of polyelectrolyte complexes by mixing two opposite charged polyelectrolytes solutions under certain conditions. In various embodiments, the mixed solution was stirred at room temperature for 2 hours to get stable complexes suspension. By carefully choosing polyelectrolytes and the conditions for complex formation, stable negatively charged polyelectrolytes complexes may be obtained for LbL film fabrication.
[0095] 2) ITO-glass or other transparent conducting substrates were cleaned with acetone, ethanol and DI water, and modified by a thin layer of linear poly(ethylenimine) (LPEI). After that, the substrates were dipped into PANI solution for 10 to 30 mins, followed by 2 times of water immersion (2 to 5 mins each time). The substrates were subsequently dipped into negatively charged polyelectrolyte complexes solution for 10 to 30 mins, followed by 2 times of water immersion (2 to 5 mins each time). The procedure may be repeated several times depending on specific requirements on film properties.
[0096] 3) After assembly, the films were naturally dried in air and heated in oven at 60°C for 30 mins.
[0097] Example 2; Approach to fabricating electrochromic device (Embodiment 2)
[0098] In some embodiments, two LbL films with compatible electrochromic properties were fabricated as described above. The two films were paired together with gel electrolyte as ionic conducting layer, and sandwiched between two electrodes:
[0099] 1) Two pieces of LPEI modified transparent conductive substrates, such as ITO coated PET or ITO coated glass slides, were used as substrates for LbL deposition as well as electrodes for electrochromic device.
[00100] 2) One electrochromic active multilayer film, such as [PANI/PSS-PEI]n, was deposited onto one of the conductive substrates.
[00101] 3) An electrolyte film was deposited onto the first electrochromic active multilayer film. Polymeric complexes PVPON-PMAA and PAA-PEO were deposited in an alternate fashion to fabricate hydrogen-bonding driven LbL film as the ionic transport layer [PVPON-PMAA/PAA-PEO]n. Without wishing to be bound by theory, it is postulated that the coil structures and large dimensions of polymeric complexes compared to single polymer
component provide loosely packed structures and greater number of free polymer segments, leading to low ionic cross-link density in the films as well as fast growing trend.
[00102] Considering the possible porous structure introduced by polymeric complexes, [PAA/PEI]n layers were deposited as protecting layers to provide continuous and smooth interfaces, and to prevent other materials from diffusing into the electrolyte layer during subsequent fabrication steps (FIG. 1). Other polymeric complexes which have good ability to carry lithium salts, such as PAA-PVPON complexes and PMAA-PEO complexes, may also be used to fabricate ionic transport layers via LbL self-assembly.
[00103] 4) Another electrochromic active multilayer film, such as [PEDOT:PSS/PEI]n, may be directly deposited on the electrolyte layer in layer-by-layer fashion.
[00104] 5) The other piece of conductive substrate may be compressed together with the multi-components layers obtained after Step 4) to constitute a functional electrochiOmic device, as showed in FIG. 2.
[00105] Example 3: Fabrication of [PA I/PAA-PEIln films and electrochromic characterizations
[00106] PAA and PEI solutions were mixed under optimized conditions with a ratio of PAA:PEI equaling to 14.7 (molar ratio calculated by polymer unit, the same hereafter). The transparent PAA and PEI solutions turned turbid immediately when mixed together, indicating the formation of complexes. The complexes were stirred for 2 hours and were filtered by 1 μπι filters before use.
[00107] PANI solution was prepared following the literature as described in Shariki S et al, Journal of Solid State Electrochemistry, 201 1, 15 (11-12), p. 2675-2681.
[00108] Linear PEI modified cleaned ITO-glasses were alternatively dipped into PAA-PEI complexes solution and PANI solution, with DI water immersion after each dipping step.
[00109] As shown in FIG. 3, the [PANI/PAA-PEI]20 films showed porous morphology. Under the same deposition conditions, [PANI/PAA-PEI]20 film was much thicker than [PANI/PAA]20 film.
[001 10] Electrochromic properties were shown in FIG. 4. The contrast of the [PANI/PAA- PEI]30 film could reach up to ΔΤ = 28.7 %, while the contrast of the [PANI/PAA]30 film was only ΔΤ = 1 1.1 %. Switching time was described as 90 % of the time taken for the completion of color conversion under kinetic test condition. Compared with the films only involving PANI and PAA, the films fabricated with PANI and PAA-PEI complexes showed
faster switching behavior with coloration time and bleaching time of 3 s and 15 s, respectively. At the same condition, coloration time and bleaching time of [PANI/PAA]30 were 6 s and 24 s, respectively.
[001 1 1] Example 4: Electrochemical characterizations of device [PANI/PSS-PEIhn II LiClOi-PC II [PEDOT:PSS/PEI n
[001 12] Two electrodes device was fabricated by pairing the [PANI/PSS-PEI]30 film and the [PEDOT:PSS/PEI]20 film, with ITO-glass on both sides as the current collector. Another device was constructed by [PANI/PSS]30 and [PEDOT:PSS/PEI]20 similarly as comparison. Gel electrolyte LiC104 in PC was used as ionic conductor. These devices were written in full cell as [PANI/PSS-PEI]30 || LiC104-PC || [PEDOT:PSS/PEI]20 and [PANI/PSS]30 || LiC104- PC II [PEDOT:PSS/PEI]20, thereafter as device-(PSS-PEI) and device-PSS. The devices operated by simultaneous oxidation of one electrochromic element and reduction of the other.
[00113] As shown in FIG. 5(A), maximum contrast of device-(PSS-PEI) was between 600 nm and 850 nm, with ΔΤ = 20 %. The maximum contrast of device-(PSS) was between 750 nm and 850 nm, with ΔΤ = 18 %. Even though the maximum contrast of these two devices was similar, device-(PSS) took much longer time than device-(PSS-PEI) to be stabilized as the voltage switched. What is more, device-(PSS) even needed more negative driven potential to get demanding bleaching status. FIG. 5(B) showed the comparison of the kinetics of both devices at 630 nm. For device-(PSS-PEI), the contrast was stable at ΔΤ = 18 % (slightly lower than mentioned above which was caused by the different testing modes involved), with the coloration time of 8 s and bleaching time of 4 s.
[001 14] Example 5: Fabrication of fPEO-PAA/PAA-PEOln solid polymer electrolyte layer
[001 15] Poly(ethylene oxide) (PEO)-PAA complexes and PAA-PEO complexes were obtained by mixing PEO and PAA solutions with different ratios of PEO and PAA. The complexes were formed based on hydrogen bonding interaction between PEO and PAA. In PEO-PAA complexes, the dominating component was PEO and the complexes worked as hydrogen bond donor during LbL self-assembly. While in PAA-PEO complexes, PAA was the dominating component and the PAA-PEO complexes worked as hydrogen bond acceptor during LbL deposition.
[001 16] The multilayer [PEO-PAA/PAA-PEO]n films were deposited by alternatively dipping the substrates into PEO-PAA complexes suspensions and PAA-PEO suspensions,
with intimidated washing steps in DI water. All the solutions were kept at pH = 3.0 and 0.1 M lithium perchlorate was added to all solutions. The films were dried overnight after fabrication, and were preserved under room temperature and room humidity for at least 3 days before test.
[001 17] For electrical characterization, the LbL films were placed between two pieces of ITO coated glass slides. Ionic conductivity values were extracted from Nyquist plot (FIG. 6). The through ionic conductivity of the [PEO-PAA/PAA-PEO]48 may reach up to 4.0 x 10"6 S/cm at room humidity, while the ionic conductivity of [PEO/PAA]48 films fabricated under the same conditions is only around 1.2 x 10"6 S/cm.
[001 18] Advantages of electrochromic active multilayer film disclosed herein include:
[001 19] 1) The specific steric configurations of polyelectrolyte complexes lead to porous structures, which promotes diffusion Of electrolyte into the electrochemical active layers and promotes ion transfer during redox reactions. The protons carried by weak polyelectrolytes could also facilitate the redox process of PANI.
[00120] 2) Large dimensions of polyelectrolyte complexes contribute to rapid fabrication of LbL films for electrochromic devices.
[00121] 3) It is the first time to propose all-solid state electrochromic devices with all components- electrochromic active layers and electrolyte layer fully based on layer-by-layer deposition. The inventors have fully taken advantage of this facile film fabricating technique- it could incorporate different kinds of materials and easily tailor the film structures, to achieve desired properties and integrate multi-functions into a layered structure device.
[00122] While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims
1. An electrochromic active multilayer film obtainable by layer-by-layer (LbL) assembly, the film comprising alternating layers of an electrochromic active material and a polyelectrolyte complex.
2. The electrochromic active multilayer film according to claim 1, wherein the film comprises 2 to 100 layers.
3. The electrochromic active multilayer film according to claim 1 or 2, wherein the film comprises 20 to 80 layers.
4. The electrochromic active multilayer film according to any one of claims 1 to 3, wherein the electrochromic active material is selected from the group consisting of polyaniline (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4- ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), poly(3,4- ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)/ poly(ethylenimine), polypyrrole, polypyridyl complexes, polymers containing viologen moieties, poly(butanyl viologen), derivatives thereof, and combinations thereof.
5. The electrochromic active multilayer film according to any one of claims 1 to 4, wherein the electrochromic active material comprises or consists of polyaniline.
6. The electrochromic active multilayer film according to any one of claims 1 to 5, wherein the polyelectrolyte complex is a negatively charged polyelectrolyte complex.
7. The electrochromic active multilayer film according to any one of claims 1 to 6, wherein the polyelectrolyte complex comprises at least one polymer having a negative net charge and at least one polymer having a positive net charge.
8. The electrochromic active multilayer film -according to any one of claims 1 to 7, wherein the polyelectrolyte complex comprises a first polymer and a second polymer,
wherein the first polymer is selected from the group consisting of poly(sodium-4- styrenesulfonate), poly(acrylic acid), copolymers thereof, and combinations thereof; and the second polymer is selected from the group consisting of poly(diallydimethylammonium chloride), poly(ethylenimine), poly(allylamine hydrochloride), copolymers thereof, and combinations thereof.
The electrochromic active multilayer film according to any one of claims 1 to 8, wherein the polyelectrolyte complex is selected from the group consisting of poly(sodium-4-styrenesulfonate)-poly(diallydimethylammonium chloride) (PSS- PDDA) complex, polystyrene sulfonate-poly(ethyleneimine) complex, poly(sodium- 4-styrenesulfonate)-poly(ethylenimine) (PSS-PEI) complex, poly(sodium-4- styrenesulfonate)-poly(allylamine hydrochloride) (PSS-PAH) complex, poly(acrylic acid)-poly(ethylenimine) (PAA-PEI) complex, poly(methacrylic acid)-polyallylamine hydrochloride (PMAA-PAH) complex, and combinations thereof.
0. The electrochromic active multilayer film according to any one of claims 1 to 9, wherein the film is porous.
1. An electrochromic device comprising one or more electrochromic active multilayer film according to any one of claims 1 to 10.
2. An electrochiOmic device comprising
a) a first electrode and a second electrode,
b) a first electrochromic active multilayer film and a second electrochromic active multilayer film, each according to any one of claims 1 to 10, and c) an electrolyte,
wherein the first electrocliromic active multilayer film and the second electrochromic active multilayer film are deposited on the first electrode and the second electrode, respectively, and then arranged facing each other with the electrolyte being sandwiched between the first electrochromic active multilayer film and the second electrochromic active multilayer film.
The electrochromic device according to claim 12, wherein the electrolyte comprises a lithium salt, preferably lithium perchl orate (LiClC^).
The electrochromic device according to claim 12 or 13, wherein the electrolyte comprises a polymer matrix.
The electrochromic device according to claim 14, wherein the polymer matrix comprises or consists of a polymer multilayer film comprising layers made of polymeric complexes.
The electrochromic device according to claim 15, wherein the polymeric complexes are selected from the group consisting of poly(N-vinylpyrrolidone)-poly(methacrylic acid) (PVPON-PMAA) complexes, poly(acrylic acid)-poly(ethylene oxide) (PAA- PEO) complexes, PAA-PVPON complexes, PMAA-PEO complexes, polyvinyl alcohol (PVA)-PVPON complexes, PVA-PEO complexes, polydopamine (PDA)- PVPON complexes, PDA-PEO complexes, PAA-polyacrylamide (PAAM) complexes, PVA-PAAM complexes, PAA-poly(N-isopropyl acrylamide) complexes, poly(N- vinylcaprolactam)-PMAA complexes, and combinations thereof.
The electrochromic device according to claim 15 or 16, wherein the polymer multilayer film comprises alternating layers of poly(N-vinylpyrrolidone)- poly(methacrylic acid) (PVPON-PMAA) complexes and poly(acrylic acid)-poly (ethylene oxide) (PAA-PEO) complexes.
The electrochromic device according to any one of claims 15 to 17, wherein the polymer multilayer film comprises alternating layers of poly(acrylic acid)-poly (ethylene oxide) (PAA-PEO) complexes and poly (ethylene oxide)-poly( acrylic acid) (PEO-PAA) complexes.
19. The electrochromic device according to claim 18, wherein unit molar ratio of PAA to PEO in the PAA-PEO complexes is about 11 :3 and PEO to PAA in the PEO-PAA complexes is about 49: 1.
20. A method of fabricating an electrochromic device using layer-by-layer assembly, the method comprising
a) depositing a first electrochromic active multilayer film and a second electrochromic active multilayer film, each according to any one of claims 1 to 10, on a first electrode and a second electrode respectively;
b) depositing an electrolyte on at least one of the first electrochromic active multilayer film or the second electrochromic active multilayer film; and c) arranging the first electrochromic active multilayer film and the second electrochromic active multilayer film facing each other with the electrolyte being sandwiched between the first electrochromic active multilayer film and the second electrochromic active multilayer film.
21. The method according to claim 20, wherein depositing the first electrochromic active multilayer film or the second electrochromic active multilayer film on the respective electrode comprises
a) depositing a first layer comprising an electrochromic active material on the respective electrode;
b) depositing a second layer comprising a polyelectrolyte complex on the first layer; and
c) optionally repeating steps a) and b) for one and more additional cycles.
22. The method according to claim 21, wherein each of steps a) and b) independently comprises contacting the deposited layer with water prior to a subsequent step.
23. The method according to claim 21 or 22, wherein steps a) and b) are carried out for 1 to 50 cycles.
24. The method according to any one of claims 21 to 23, wherein depositing an electrolyte on at least one of the first electrochromic active multilayer film or the second electrochromic active multilayer film comprises
a) depositing a first layer comprising a first polymeric complex on the respective electrode;
b) depositing a second layer comprising a second polymeric complex on the first layer; and
c) optionally repeating steps a) and b) for one and more additional cycles.
25. The method according to claim 24, wherein steps a) and b) carried out for 1 to 50 cycles.
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