Processes for preparing ion-conducting PVB materials and films and associated materials, films, and devices

Abstract

Processes for forming polyvinyl butyral (PVB) materials, PVB materials such as PVB interlayers, and associated devices and products are disclosed. A process according to some embodiments may include combining polymer resin and one or more plasticizers to form a first combination. The one or more plasticizers may include one or more oxygenated organic compounds that are liquid at about 20 °C. The process may also include combining one or more lithium salts and one or more solvents to form a second combination. The one or more solvents may have a dielectric constant greater than about four (4) and less than about 100 at about 20 °C. The process may also include combining the first combination and the second combination to obtain a material, forming a layer of the material, and exposing the layer to a temperature of about 75 °C to about 150 °C.

Description

PROCESSES FOR PREPARING ION-CONDUCTING PVB MATERIALS ANDFILMS AND ASSOCIATED MATERIALS, FILMS, AND DEVICESTECHNICAL FIELD

[0001] The present disclosure relates in general to ion-conducting polymers, and in particular to their application as an electrolyte material or an ion-conducting material in electrochromic devices.BACKGROUND

[0002] “Smart windows” or “smart glass” may refer to devices where the colour and the amount of light transmission or reflection of the device may be altered by electronic switching. When the bias is electrical in nature (for example, a voltage is applied), the devices may be referred to as electrochromic (EC) devices. These devices may be used for variable transmission windows for use in buildings and transportation (automobiles, aeroplanes, passenger trains, boats such as ferries, etc.), displays, and automotive mirrors for controlling reflectivity. By adjusting the transmission of the windows, the solar energy that is transmitted through the window may also change.

[0003] Windows are widely regarded to be one of the least efficient components of a building envelope. Heating, ventilating, and air conditioning (HVAC) and lighting in buildings account for greater than 30 percent of global primary energy consumption, and up to half of this energy can be lost through windows. This energy loss results in high greenhouse gas (GHG) emissions and costs for building owners. The use of electrochromic windows in residential and commercial buildings may result in buildings with improved energy efficiency. Electrochromic windows can lower building heating, cooling and lighting needs by about 20%. In addition, electrochromic windows may provide shade, glare reduction, and provide other benefits, such as improved worker productivity.

[0004] Electrochromic glass (also known as electrochromic glazing) in the automotive industry may be used in small surface rear-view and side-mirrors. The automotive industry is interested in expanding the products into sunroofs and side windows to improve the passenger experience (particularly as ridesharing puts morepassengers in the back seat). Air conditioning and heating systems cool, heat, and ventilate the interior of vehicles. These air conditioning and heating systems may be electrically powered, and their use can particularly reduce electric vehicle (EV) range by 30-40%, depending upon the air conditioning and heating systems, the climate, and the driving cycle. Electrochromic windows can help manage the interior climate of vehicles, thus reducing air conditioning and heating usage, and extending the range of EVs. Therefore, when used in transportation, electrochromic windows may result in vehicles with improved energy efficiency.

[0005] Laminated glass is commonly used in windows, skylights and automotive windshields, as well as other applications where regulatory codes mandate the use of safety glass. Laminated glass has an interlayer which permanently bonds the glass pieces together, offering improved structural properties and impact resistance.

[0006] Polyvinyl butyral (PVB) is a popular interlayer for laminated windows due to its optical clarity, ability to adhere to many surfaces, its low cost and ease of manufacture.

[0007] Glass with a PVB interlayer usually requires the use of an autoclave in the lamination process, wherein both heat and pressure are required processing steps. Commonly, a PVB interlayer is positioned between two pieces of glass, the materials are suctioned together and de-aired before being introduced into an autoclave.

[0008] PVB is a reasonable choice for the ionically conductive interlayer for electrochromic devices due to its demonstrated utility as suitable interlayer in nonionic conductive applications.

[0009] No admission is necessarily intended, nor should be construed, that any of the preceding information constitutes prior art.SUMMARY

[0010] In some aspects, the techniques described herein relate to a process including: combining polyvinyl butyral (PVB) polymer resin and one or more plasticizers to form a first combination, the one or more plasticizers including one or more oxygenated organic compounds that are liquid at about 20 °C; combining one or more lithium salts and one or more solvents to form a second combination, the one or more solvents having a dielectric constant greater than about four (4) and less than about 100 at about 20 °C; combining the first combination and the second combination to obtain a material; forming a layer of the material; and exposing the layer to a temperature of about 75 °C to about 150 °C.

[0011] In some aspects, the techniques described herein relate to a process wherein the material includes from about 15 wt% to about 45 wt% of the PVB polymer resin, about 15 wt% to about 50 wt% of the one or more plasticizers, about 5 wt% to about 15 wt% of the one or more lithium salts, and about 15 wt% to about 35 wt% of the one or more solvents, the material is a liquid material, forming the layer of the material includes forming a wet film of the liquid material, and exposing the layer to a temperature of about 75 °C to about 150 °C includes exposing the wet film to a temperature of about 75 °C to about 150 °C.

[0012] In some aspects, the techniques described herein relate to a process wherein the material includes from about 45 wt% to about 60 wt% of the PVB polymer resin, about 15 wt% to about 25 wt% of the one or more plasticizers, about 10 wt% to about 20 wt% of the one or more lithium salts, and about 5 wt% to about 25 wt% of the one or more solvents, the material is a solid or semi-solid material, forming the layer of the material includes forming a layer of the solid or semi-solid material, and exposing the layer to a temperature of about 75 °C to about 150 °C includes exposing the layer of the solid or semi-solid material to a temperature of about 75 °C to about 150 °C.

[0013] In some aspects, the techniques described herein relate to a process wherein the PVB polymer resin includes from about 1 wt% to about 4 wt% of polyvinyl acetate, from about 11 wt% to about 21 wt% of polyvinyl alcohol, and from about 75 wt% to about 88 wt% of acetal.

[0014] In some aspects, the techniques described herein relate to a process wherein the one or more oxygenated organic compounds include one or more of dimethyl glutarate, dimethyl 2-methylglutarate, dimethyl adipate, and diethylene glycol dibutyl ether.

[0015] In some aspects, the techniques described herein relate to a process wherein the one or more lithium salts include one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate, and lithium difluoro(oxalato)borate.

[0016] In some aspects, the techniques described herein relate to a process wherein the one or more solvents include one or more of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate.

[0017] In some aspects, the techniques described herein relate to a process wherein the material includes the one or more oxygenated organic compounds and the one or more solvents in a mass ratio of about 1 :1 , about 2.5:1 , about 5:1 , or about 1 :2.

[0018] In some aspects, the techniques described herein relate to a process wherein the material further includes an additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof.

[0019] In some aspects, the techniques described herein relate to a process wherein the material is a liquid material, forming the layer of the material includes applying the liquid material onto a first release liner to form a wet film on the first release liner, and the process further includes: placing a second release liner such that the second release liner contacts the wet film; and applying pressure to the wet film while exposing the wet film to a temperature of about 75 °C to about 150 °C to form an ion-conducting film between the first release liner and the second release liner.

[0020] In some aspects, the techniques described herein relate to an ionconducting material formed according to the processes described herein.

[0021] In some aspects, the techniques described herein relate to an electrochromic device manufactured using an ion-conducting material formed according to the processes described herein.

[0022] In some aspects, the techniques described herein relate to a process wherein the material is a liquid material, forming the layer of the material includes applying the liquid material onto a first electrochromic layer carried by a first transparent substrate to form a wet film on the first electrochromic layer, and the process further includes: placing a second transparent substrate carrying a second electrochromic layer complementary to the first electrochromic layer on the wet film such that the second electrochromic layer contacts the wet film; exposing the first transparent substrate, the first electrochromic layer, the wet film, the second electrochromic layer, and the second transparent substrate to the temperature of about 75 °C to about 150 °C to form an ion-conducting layer between the first electrochromic layer and the second electrochromic layer; and applying a seal around a perimeter of the ion-conducting layer.

[0023] In some aspects, the techniques described herein relate to an electrochromic device formed according to the processes described herein.

[0024] In some aspects, the techniques described herein relate to a process including: combining one or more plasticizers, one or more lithium salts, and one or more solvents to obtain a solution, the one or more plasticizers including one or more oxygenated organic compounds that are liquid at about 20 °C, the one or more solvents having a dielectric constant greater than about four (4) and less than about 100 at about 20 °C; exposing polyvinyl butyral (PVB) polymer resin to a temperature of about 40 °C to about 60 °C; combining the solution and the PVB polymer resin to form a mixture; melting the mixture; and forming an ion-conducting film of the mixture.

[0025] In some aspects, the techniques described herein relate to a process wherein combining the solution and the PVB polymer resin to form the mixtureincludes combining the solution and the PVB polymer resin to form the mixture in an atmosphere of less than about 1000 parts per million water.

[0026] In some aspects, the techniques described herein relate to a process wherein the mixture includes from about 45 wt% to about 60 wt% of the PVB polymer resin, about 15 wt% to about 25 wt% of the one or more plasticizers, about 10 wt% to about 20 wt% of the one or more lithium salts, and about 5 wt% to about 25 wt% of the one or more solvents.

[0027] In some aspects, the techniques described herein relate to a process wherein the PVB polymer resin includes from about 1 wt% to about 4 wt% of polyvinyl acetate, from about 11 wt% to about 21 wt% of polyvinyl alcohol, and from about 75 wt% to about 88 wt% of acetal.

[0028] In some aspects, the techniques described herein relate to a process wherein the one or more oxygenated organic compounds include one or more of dimethyl glutarate, dimethyl adipate, dimethyl-2-methyl glutarate, and diethylene glycol dibutyl ether.

[0029] In some aspects, the techniques described herein relate to a process wherein the one or more lithium salts include one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate.

[0030] In some aspects, the techniques described herein relate to a process wherein the one or more solvents include one or more of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate.

[0031] In some aspects, the techniques described herein relate to a process wherein the mixture includes the one or more plasticizers and the one or more solvents in a mass ratio of about 1 :1 or about 7:3.

[0032] In some aspects, the techniques described herein relate to a process wherein the mixture further includes an additive selected from fillers, ultravioletstabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof.

[0033] In some aspects, the techniques described herein relate to a process wherein forming an ion-conducting film of the mixture includes extruding the mixture to form the ion-conducting film.

[0034] In some aspects, the techniques described herein relate to an ionconducting film formed according to the processes described herein.

[0035] In some aspects, the techniques described herein relate to an electrochromic device manufactured using an ion-conducting film formed according to the processes described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The specific arrangements shown in the Figures should not be viewed as limiting. It should be understood that the illustrated elements, including the shape, size and scale, may not necessarily be drawn in actual proportion to each other.

[0037] Further features and advantages of the present disclosure will become apparent from the following detailed description, taken in combination with the appended drawings, in which:

[0038] Fig. 1 is a schematic representation of an electrochromic device that may be manufactured using PVB ion-conducting materials that are formed using methods in accordance with some embodiments.

[0039] Figs. 2 to 9 are graphs showing the change in CIE Y transmittance for the bleached and colored states over repeated cycles for the electrochromic devices obtained in Examples 1 to 8, in accordance with some embodiments.

[0040] Fig. 10A is a flow diagram depicting a process for forming an ion-conducting material according to various embodiments.

[0041] Fig. 10B is a flow diagram depicting a process for forming an ion-conducting film according to various embodiments.

[0042] Fig. 10C is a flow diagram depicting a process for forming an electrochromic device according to various embodiments.

[0043] Fig. 11 is a flow diagram depicting a process for forming an ion-conducting film according to various embodiments.

[0044] Fig. 12A is a schematic representation of a curved electrochromic device that may be manufactured using PVB ion-conducting materials that are formed using processes in accordance with some embodiments.

[0045] Fig. 12B is a schematic representation of a flat electrochromic device that may be manufactured using PVB ion-conducting materials that are formed using processes in accordance with some embodiments.

[0046] Throughout the drawings, like reference numerals will be understood to refer to like parts, components, and structures.DETAILED DESCRIPTION

[0048] In various embodiments, the term “anodic electrochromic layer” may refer to a layer comprising a solid-state inorganic electrochromic material that transitions to its coloured state when ions are extracted. The anodic electrochromic layer may be located parallel to and positioned in between an electrically conductive layer and a solid-state, ion-conductive electrolyte layer within an electrochromic device.

[0049] In various embodiments, the term “cathodic electrochromic layer” may refer to a layer comprising a solid-state inorganic electrochromic material that transitions to its coloured state when ions are inserted. The cathodic electrochromic layer may be located parallel to and positioned in between an electrically conductive layer and an ion-conducting layer within an electrochromic device.

[0050] In various embodiments, the term “cross linker” may refer to an additive which may link two entities by covalent or ionic bonds, which may alter the mechanical properties or viscosity of the material by reacting two different components.

[0051] In various embodiments, the term “cycled” may refer to the application of a bias voltage across an electrochromic device by an external power source such as a battery or a potentiostat, and then, after a prescribed time, reversing the polarity. The reversed polarity may have a different voltage than the original bias voltage. The bias polarity is again reversed, and a “cycle” is complete.

[0052] In various embodiments, the term “electrochromic device” may refer to a device comprising a substrate, an anodic electrode, a cathodic electrode, an ion- conductive layer, charge-balancing ions, and another substrate. The device may be capable of transitioning transparency from a coloured state (low transmittance of light, such as transmittance below about 25% to about 30% CIE Y) to a transparent state (high transmittance of light, such as transmittance above about 60% to about 80% CIE Y ), and / or from a transparent state to a coloured state, through the use of an applied electrical bias. The “transparent” state may also be referred to as a “bleached” state.

[0053] In various embodiments, the term “electrode” may refer to a solid-state, layered structure comprising of a substrate, an electrically conductive layer and an electrochemically active layer parallel and in contact with each other.

[0054] In various embodiments, the term “interlayer” may refer to a layer (of material) placed between other layers.

[0055] In various embodiments, the term “ion-conducting” may refer to the ability of a material to shuttle ions between different locations. As an example, the ionconducting material described herein in various embodiments is capable of shuttling lithium ions between the anode and cathode upon the introduction of an external electrical bias.

[0056] In various embodiments, the term “photodeposition” may refer to the process where chemical precursors that have been solution-deposited onto a substrate, electrode, or substrate-supported electrode, are exposed to ultraviolet (UV) or near-infrared (NIR) electromagnetic radiation, or a combination thereof (in the presence or absence of ozone), resulting in the photochemical conversion to an inorganic, oxide layer.

[0057] In various embodiments, the term "substrate" may refer to a mechanically supportive material upon which additional functional layers may be assembled, placed, or positioned.

[0058] The present disclosure describes ion-conducting PVB materials formed from polyvinyl butyral (PVB) polymer resin, one or more plasticizers, one or more lithium salts, and one or more solvents. The one or more plasticizers may include one or more oxygenated organic compounds that are liquid at about 20 °C. The one or more oxygenated organic compounds may be suitable esters, such as methyl diesters, suitable ethers, such as glycol ethers, suitable carboxylic acids, or other suitable oxygenated organic compounds that are liquid at about 20 °C.

[0059] In some embodiments, the one or more oxygenated organic compounds include one or more of di-n-butyl phthalate, diisononyl phthalate, bis(2-ethylhexyl) phthalate, di(2-ethylhexyl) adipate, diisodecyl adipate, tricresyl phosphate, acetyl tributyl citrate, tributyl citrate, polyester-based plasticizers, epoxidized soybean oil,diethylene glycol dibenzoate, and bio-based plasticizers (for example, castor oil derivatives). In various embodiments, the one or more plasticizers may include one or more of phthalate plasticizers, adipate plasticizers, phosphate plasticizers, citrate plasticizers, polyester plasticizers, epoxy plasticizers, and glycol ether-based plasticizers.

[0060] The one or more solvents may have a dielectric constant (&) greater than about four (4) and less than about 100 at about 20 °C. In some embodiments, the one or more solvents have a dielectric constant greater than about 100 at about 20 °C.

[0061] These ion-conducting PVB materials can advantageously set (harden) without crosslinkers at low temperatures and at ambient pressures.

[0062] The ion-conducting PVB materials described herein display sufficient ionic conductivity and optical transparency. Moreover, the ion-conducting PVB materials have high mechanical strength, and show stability to temperature, ultraviolet light and potential chemical and electrochemical side reactions. Furthermore, the ionconducting PVB materials may be manufactured using cost-effective and scalable processes.

[0063] The present disclosure also relates to ion-conducting PVB films that may be prepared via low temperature and ambient pressure fabrication processes. In some embodiments, the ion-conducting PVB films may be employed as an electrolyte layer in electrochromic devices such as electrochromic sunroofs. In some embodiments, the ion-conducting PVB films may be prepared using manufacturing techniques such as extrusion.

[0064] The common fabrication method for the incorporation of ion-conducting PVB interlayers in an electrochromic device normally requires the use of an autoclave, wherein the material is subject to high pressure (8-12 bar) at temperatures of 100- 150 degrees Celsius.

[0065] Disclosed herein is an ion-conducting PVB material that can, surprisingly, set (harden) when exposed to low temperature heating (less than about 150 °C) and ambient pressure, without the addition of cross linkers or hardeners to theformulation. This ion-conducting PVB material may be formed from PVB polymer resin, one or more plasticizers, one or more lithium salts, and one or more solvents. The one or more plasticizers may include one or more oxygenated organic compounds that are liquid at about 20 °C. The one or more oxygenated organic compounds may be suitable esters such as methyl diesters or suitable ethers such as glycol ethers. The one or more solvents may have a dielectric constant greater than about four (4) and less than about 100 at about 20 °C.

[0066] In some embodiments, the PVB ion-conducting material comprises about 15 wt% to about 45 wt% the PVB polymer resin, about 15 wt% to about 50 wt% the one or more plasticizers, about 5 wt% to about 15 wt% the one or more lithium salts, and about 15 wt% to about 35 wt% the one or more solvents.

[0067] In certain embodiments, the ion-conducting PVB material further comprises at least one additive. In certain embodiments, the additive is selected from at least one of fillers, ultraviolet stabilizers, heat stabilizer, adhesion improvers, antioxidants, radical scavengers, ultraviolet light absorbers, or any combination thereof.

[0068] PVB is a random copolymer. PVB materials may be described with reference to one or more of molecular weight (MW), percent polyvinyl alcohol content (percent alcohol groups), or percent polyvinyl acetate content (amount of acetalization). The properties of PVB materials vary with different percentages of these groups, along with their molecular weight. In some embodiments, the PVB polymer resin comprises a polyvinyl acetate content of about 1 wt% to about 4 wt%, a polyvinyl alcohol content of about 11 wt% to about 21 wt%, and an acetal content of about 75 wt% to about 88 wt%.

[0069] The ion-conducting PVB material described herein comprises one or more salts in an amount sufficient to impart high ionic strength to the material. In some embodiments, the one or more salts are one or more lithium salts selected from one of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate, or any combination thereof. In some embodiments, the one or more salts are one or more lithium salts selected from one of lithium perchlorate,lithium bis(trifluoromethanesulfonyl)imide, lithium triflate, or lithium bis(oxalato)borate or any combination thereof.

[0070] As demonstrated in the present disclosure, it has been found that low temperature setting was observed when the one or more plasticizers was at least partially comprised of one or more methyl diester solvents. In some embodiments, the one or more plasticizers include at least one of dimethyl glutarate, dimethyl 2- methylglutarate, and dimethyl adipate. In some embodiments, the methyl diester solvent component comprises dimethyl adipate. In some embodiments, the methyl diester solvent component comprises dimethyl glutarate and dimethyl 2- methylglutarate. In some embodiments, the one or more plasticizers includes a glycol ether such as diethylene glycol dibutyl ether.

[0071] The one or more solvents may have a dielectric constant greater than about four (4) and less than about 100 at about 20 °C to help facilitate the dissociation of the one or more salts. In some embodiments, the one or more solvents include at least one of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate. In some embodiments, the one or more solvents have a dielectric constant less than about 100 at about 20 °C.

[0072] In some embodiments, the ion-conducting PVB material is formed from a methyl diester solvent and propylene carbonate.

[0073] In some embodiments, the ion-conducting PVB material is formed from a methyl diester component and propylene carbonate in a 1 : 1 , 2.5: 1 , 5: 1 or 1 :2 mass ratio.

[0074] The present disclosure also relates to use of the ion-conducting PVB materials in forming electrochromic devices. In some embodiments, ion-conducting PVB material is utilized to form an ion-conducting PVB film for use in the manufacture of an electrochromic device.

[0075] Fig. 1 is a schematic representation of an electrochromic device 10 that includes a PVB ion-conducting layer formed in accordance with various embodiments. The electrochromic device 10 has a multilayer architecture. The electrochromic device 10 includes a first transparent substrate 1 , a first transparentconductive layer 2, an anodic electrochromic layer 3 (which may be referred to as an ion-storage layer), an ion-conductive electrolyte layer 4 formed according to embodiments described herein, a cathodic electrochromic layer 5, a second transparent conductive layer 6, and a second transparent substrate 7.

[0076] The first transparent substrate 1 and the second transparent substrate 7 provide a base structure for the active device materials and protection from both sides. The first transparent conductive layer 2 and the second transparent conductive layer 6 provide a means for conducting charge to and from the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 from an external power source 8 and / or control electronics and software. The ion-conductive electrolyte layer 4 provides a means to transport ions between the anodic electrochromic layer 3 and the cathodic electrochromic layer 5, which induces color changes in the anodic electrochromic layer 3 and the cathodic electrochromic layer 5. The order of the layers may be reversed with respect to the substrate. That is, the layers can be in the following order: first transparent substrate 1 , first transparent conductive layer 2, cathodic electrochromic layer 5, ion-conductive electrolyte layer 4, anodic electrochromic layer 2, second transparent conductive layer 6, and second transparent substrate 7. Additional protective and functional layer(s) (not illustrated in Fig. 1 ) may also optionally be included in the electrochromic device 10. The thickness of the layers of the electrochromic device 10, including the shape, size and scale of layers may not necessarily be drawn to scale or in actual proportion to each other, but is schematically represented for clarity.

[0077] In various embodiments, the electrochromic device 10 comprises at least one electrochromic material comprising an electrochromic metal oxide fabricated by i) spray coating a substrate containing a transparent conductive coating with a solution of one or more inorganic or organometallic precursors; and ii) exposing the coated substrate to at least one of infrared (IR) radiation, ultraviolet (UV) radiation, ozone or a combination thereof to convert the one or more precursors to an electrochromic metal oxide film.

[0078] In some embodiments, the inorganic or organometallic precursor is a chemical compound that contains a metal that can be converted into a metal oxide upon exposure to IR radiation, UV radiation, or ozone. Typical examples include, butare not limited to an inorganic chloride, an inorganic nitrate, an organometallic 2- ethylhexanoate, an organometallic butoxide, an organometallic ethoxide, an organometallic methoxide, an organometallic isopropoxide, an organometallic acetylacetonate, an organometallic silanolate, an organometallic oxalate, or mixtures thereof. Examples of compatible solvents suitable for preparing the precursor solution include but are not limited to water, methanol, ethanol, isopropanol, acetone, hexane, acetylacetone, methyl isobutyl ketone, propylene glycol methyl ether acetate (PGMEA), ethyl acetate, acetonitrile, ethylene glycol, tetrahydrofuran (THF), toluene, and N-methylpyrrolidone.

[0079] In various embodiments of an electrochromic device, the transparent conductive substrate may include a cathodic electrochromic layer and, and the second transparent conductive substrate may include an anodic electrochromic layer. Further, such embodiments, the cathodic electrochromic layer may include tungsten oxide or doped tungsten oxide, the first transparent, electrically conductive layer may include indium tin oxide (ITO) or fluorine tin oxide (FTO), the anodic electrochromic layer may include nickel oxide or doped nickel oxide, and the second transparent, electrically conductive layer may include ITO or FTO. The anodic electrochromic layer and cathodic electrochromic layer are separated by an ionconducting electrolyte layer. The ion-conducting electrolyte layer may be an ionconducting PVB layer, as described herein, formed from PVB polymer resin, one or more lithium salts, one or more plasticizers including one or more oxygenated organic compounds that are liquid at about 20 °C, and one or more solvents having a dielectric constant greater than about four (4) and less than about 100 at about 20 °C. Alternatively, the configuration of the electrodes may be reversed in a representative electrochromic device such that the first transparent conductive substrate includes an anodic electrochromic layer, while the second transparent conductive substrate includes a cathodic electrochromic layer.

[0080] U.S. Patent Publication No. US20200165161A1 , the publication of U.S. Patent Application No. 16 / 632,636, titled “PHOTODEPOSITION OF METAL OXIDES FOR ELECTROCHROMIC DEVICES,” describes photodeposition techniques for generating metal oxides and mixed-metal oxides for making electrochromic layers and devices. The entire disclosure of U.S. Patent Publication No.US20200165161A1 is incorporated herein by reference in jurisdictions allowing such incorporation.

[0081] The first transparent substrate 1 and the second transparent substrate 7 may each include, but are not limited to glass, plastic, or polymers. The transparent substrates should have suitable optical, electrical, thermal, and mechanical properties for the desired application. In some embodiments, the transparent substrates are comprised of glass, polyethylene terephthalate (PET), polycarbonate, polyethylene naphthalate (PEN), or polyvinyl butyral (PVB). The first transparent substrate 1 and the second transparent substrate 7 may be of the same material or different materials. In some embodiments, both transparent substrates are glass. If the substrates are made of soda-lime glass, the substrates may include a sodium barrier layer. In other embodiments, both transparent substrates are tempered glass. In other embodiments, both transparent substrates are polycarbonate.

[0082] In some embodiments, the transparent substrates are independently glass, polycarbonate, or polyethylene terephthalate. The substrates may be planar, curved, doubly curved, or complex curved.

[0083] The first transparent conductive layer 2 and the second transparent conductive layer 6 typically are or are formed from films comprising a transparent conductive oxide (TCO). The conductive coatings should provide sufficient conductance for the electrochromic device and should not appreciably interfere with the transmission of light. The first transparent conductive coating and the second transparent conductive coating may be of the same material or different materials. In some embodiments, the transparent conductive coating may include fluorine tin oxide (FTO), indium tin oxide (ITO), aluminum zinc oxide (AZO), silver mesh, silver nanowires, silver nanoparticles, carbon nanotubes, carbon black, graphene, conductive polymers, or mixtures of two or more thereof. In some embodiments, the transparent conductive coating includes FTO or ITO.

[0084] The anodic electrochromic layer 3 and the cathodic electrochromic layer 5 may exhibit a high color contrast between their colored and bleached states, may have rapid conversion between coloured and bleached states, may be capable ofswitching at low applied voltage, and may show excellent reversibility with cycling between states.

[0085] There are different types of electrochromic materials including organic dyes and surface-confined electrochromic layers, such as metal oxides. The majority of the architectural electrochromic windows on the market today employ metal oxides, as the metal oxides are more durable than their organic counterparts, and generally switch more uniformly when used on larger area windows.

[0086] Tungsten oxide (“WOx”) is a well-known cathodic electrochromic material that cycles between a pale yellow (or transparent) fully oxidized state and deep blue partially reduced state in electrochromic devices. The transparent film can be electrochemically reduced in the presence of lithium ions to form the coloured, reduced state (“LiWOx”), and reversibly re-oxidized to the transparent state. Typical fabrication methods of WOx thin films include sputtering, evaporation, and calcination of solution-based tungsten oxide precursors. Examples of other electrochromic cathodic materials include, but are not limited to, molybdenum oxide (“MoOx”), titanium oxide (“TiOx”), tantalum oxide (“TaOx”), and niobium oxide (“NbOx”).

[0087] Nickel oxide (“NiOx”) is a known anodic electrochromic material that colours complementary to tungsten oxide to create a darker, more neutral coloured dark state in the electrochromic cell. Deposition of NiOx films is typically performed by sputtering. Another example of an anodic electrochromic material is iridium oxide (“IrOx”). Materials such as cobalt oxide (“CoOx”), manganese oxide (“MnOx”) and iron oxide (“FeOx”) have also been shown to exhibit electrochromic behaviour, but may not be ideal as they do not bleach sufficiently. Vanadium oxide (“VOx”) is another well-known anodic electrochromic material.

[0088] In some embodiments, the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 each comprise metal oxides selected from the group consisting of NiOx, WOx, MoOx, TiOx, TaOx, VOx, NbOx, CoOx, IrOx, MnOx, FeOx, LiNiOx, WNbOx, TiWOx, LiWOx, NiNbOx, NiNbLiOx, NiAILiOx, or combinations thereof. In some embodiments, the cathodic electrochromic layer 5 includes WOx, WNbOx, TiWOx, LiWOx, or combinations thereof. In some embodiments, the anodicelectrochromic layer 3 includes NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, VOx, or combinations thereof. In some embodiments, each of the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 is predominantly composed of tungsten oxide. In some embodiments, each of the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 is predominantly composed of nickel oxide.

[0089] In some embodiments, the anodic electrochromic layer 3 is a doped metal oxide, and the dopant atom is selected from niobium, aluminum, cerium, lithium, tantalum, molybdenum, cobalt and titanium.

[0090] Each of the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 may have an average thickness of 10 nm to 2000 nm. In some embodiments, each of the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 have an average thickness of 100 nm to 800 nm. In some embodiments, the average thickness of each of the anodic electrochromic layer 3 and the cathodic electrochromic layer 5 is 200 nm to 700 nm.

[0091] In certain embodiments, an additional layer is added to at least one of the anodic electrochromic layer 3 and the cathodic electrochromic layer 5. In certain embodiments, this additional layer is a barrier layer. In certain embodiments, this additional barrier layer comprises niobium oxide, lithium oxide, titanium oxide, tantalum oxide, cerium oxide, aluminum oxide, or a mixture thereof. In certain embodiments, the barrier layer comprises niobium oxide, lithium oxide, or a mixture thereof.

[0092] One function of an electrolyte layer in an electrochromic device is to allow ions and current to travel between anode and cathode materials. In some embodiments, the ion-conducting PVB material described herein is employed as the electrolyte layer in an electrochromic device.

[0093] In accordance with some embodiments, a process for forming an ionconducting PVB film comprises combining and stirring a first mixture comprising PVB polymer resin and one or more plasticizers that include one or more oxygenated organic compounds that are liquid at about 20 °C, and a second mixture comprising one or more lithium salts in one or more solvents having a dielectric constant greater than about four (4) and less than about 100 at about 20 °C. In some embodiments,the one or more solvents have a dielectric constant greater than about 4 and less than about 100 at about 20 °C. Stirring continues until a clear liquid ion-conducting PVB material is formed, which is then formed into a film. The film is then exposed to a temperature of about 75 °C to about 150 °C at ambient pressure.

[0094] In some embodiments, the ion-conducting PVB film is exposed to a temperature of between 75 °C and 150 °C at ambient pressure. In other embodiments, the PVB ion-conducting material is exposed to a temperature of 80 °C for 2 hours. In other embodiments, the ion-conducting PVB material is exposed to a temperature of 100 °C for 1 hour. In other embodiments, the ion-conducting PVB material is exposed to a temperature of 130 °C for 0.5 hours. These heating steps may be conducted at atmospheric pressure.

[0095] According to some embodiments, the ion-conducting PVB material can be applied onto a substrate or an electrode to form an ion-conducting PVB film by pouring, painting, casting, extrusion, a drawdown process, another process, or a combination of the preceding processes. The process can be repeated until a film of the desired thickness is obtained.

[0096] In some embodiments, the substrate is a transparent substrate coated with a transparent conductive coating and an electrochromic metal oxide layer. In these embodiments, the ion-conducting PVB film coated substrate can be incorporated directly into an electrochromic device.

[0097] In other embodiments, the PVB film is formed by applying the ionconducting PVB material onto a release liner or between two release liners. The material is cooled to room temperature, removed from between the release liners, and the PVB ion-conducting sheet is cut to size and incorporated between two substrates or electrodes.

[0098] In some embodiments, the ion-conducting PVB material has an average thickness of about 25 pm to about 2000 pm. In other embodiments, the ionconducting PVB material has an average thickness of about 50 pm to about 1000 pm.

[0099] Operating conditions of electrochromic windows are typically in the range of about -20 °C to about 85 °C. Hence, a polymer may be utilized that does not change (appreciably soften or crystallize) in the thermal range of application. The ionconducting PVB material disclosed herein does not soften considerably at about 80 °C to about 100 °C after initial set (harden).

[0100] In a representative electrochromic device, the transparent conductive substrate may include a cathodic electrochromic layer, and the second transparent conductive substrate may include an anodic electrochromic layer. Further, in such an embodiment, the cathodic electrochromic layer may include tungsten oxide or doped tungsten oxide, the first transparent, electrically conductive layer may include ITO or FTO, the anodic electrochromic layer may include nickel oxide or doped nickel oxide, and the second transparent, electrically conductive layer may include ITO or FTO. The anodic electrochromic layer and cathodic electrochromic layer are separated by an ion-conducting electrolyte layer. The ion-conducting electrolyte layer may be an ion-conducting PVB layer formed as described herein. Alternatively, the configuration of the electrodes may be reversed in a representative electrochromic device such that the first transparent conductive substrate includes an anodic electrochromic layer, while the second transparent conductive substrate includes a cathodic electrochromic layer.

[0101] Specific examples are described. It will be understood that the following examples are intended to describe various embodiments and are not intended to be limiting in any way. It will be understood that certain aspects of the disclosed processes can be arranged and combined in a wide variety of different configurations, all of which are contemplated herein.EXAMPLESExample 1

[0102] In a first container, 15 g of polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was added to a 50 g plasticizer blend of dimethyl adipate and dimethyl-2- methyl glutarate (Solvay). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 15 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) was dissolved in 20 g propylene carbonate(Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 100 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 15:50:15:20.

[0103] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a twelve inch by twelve inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with tungsten oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0104] A second twelve inch by twelve inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, nickel oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 100 °C convection oven, for one (1) hour. The device was removed from the oven and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external polyisobutylene (PIB) seal (Helioseal).

[0105] The laminate device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 300 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 75% and the coloured state had a transmittance of 25% over 1000 cycles. Fig. 2 shows over 1485 switching cycles for the device.Example 2

[0106] In a first container, 0.75 g of polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was added to a 2.5 g plasticizer blend of dimethyl adipate and dimethyl-2- methyl glutarate (Solvay). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 0.75 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) was dissolved in 1 g propylene carbonate(Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 5 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 15:50:15:20.

[0107] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a four inch by four inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with tungsten oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0108] A second four inch by four inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, nickel oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 150 C hotplate, for one (1) hour. The device was removed and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external PIB seal (Helioseal).

[0109] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 240 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 72% and the coloured state had a transmittance of 20%. Fig. 3 shows 1350 switching cycles for the device, with transmittance data measured during cycles 1 to 200 and cycles 1150 to 1350.Example 3

[0110] In a first container, 0.375 g of polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was added to 1 .25 g of dimethyl glutarate (Sigma Aldrich). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 0.375 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) wasdissolved in 0.5 g propylene carbonate (Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 2.5 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 15:50:15:20.

[0111] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with nickel oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0112] A second two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, tungsten oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 100 °C hotplate, for one (1) hour. The device was removed and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external PIB seal (Helioseal).

[0113] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 180 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 76% and the coloured state had a transmittance of 26%. Fig. 4 shows 750 switching cycles for the device.Example 4

[0114] In a first container, 0.475 g of polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was added to 1 .2 g of dimethyl glutarate (Sigma Aldrich). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 0.375 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) wasdissolved in 0.475 g propylene carbonate (Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 2.5 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 19:48:14:19.

[0115] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with nickel oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0116] A second two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, tungsten oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 100 °C convection oven, for one (1) hour. The device was removed from the oven and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external PIB seal (Helioseal).

[0117] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 180 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 72% and the coloured state had a transmittance of 26%. Fig. 5 shows 500 switching cycles for the device.Example 5

[0118] In a first container, 0.875 g of polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was added to a 0.425 g plasticizer blend of dimethyl adipate and dimethyl- 2-methyl glutarate (Solvay). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 0.325 g of lithiumbis(trifluoromethylsulfonyl)imide (Gelon) was dissolved in 0.8775 g propylene carbonate (Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 2.5 g of electrolyte (ionconducting) material with PVB: Plasticizer: Li salt: PC mass percent ratio of 35:17:13:35.

[0119] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with tungsten oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0120] A second two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, nickel oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 100 °C convection oven, for one (1) hour. The device was removed from the oven and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external PIB seal (Helioseal).

[0121] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 180 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 72% and the coloured state had a transmittance of 30%. Fig. 6 shows 210 switching cycles for the device, with transmittance data measured during cycles 1 to 50 and cycles to 200 to 210.Example 6

[0122] In a first container, 0.75 g of polyvinyl butyral (PVB) resin (Mowital B 30 HH, Kuraray) was added to a 2.5 g plasticizer blend of dimethyl adipate and dimethyl-2-methyl glutarate (Solvay). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 0.75 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) was dissolved in 1 g propylene carbonate (Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 5 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 15:50:15:20.

[0123] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with tungsten oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0124] A second two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, nickel oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 100 °C convection oven, for one (1) hour. The device was removed from the oven and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external PIB seal (Helioseal).

[0125] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 180 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 66% and the coloured state had a transmittance of 18%. Fig. 7 shows 50 switching cycles for the device.Example 7

[0126] In a first container, 0.75 g of polyvinyl butyral (PVB) resin (Mowital B 55 HH, Kuraray) was added to a 2.5 g plasticizer blend of dimethyl adipate and dimethyl-2-methyl glutarate (Solvay). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 0.75 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) was dissolved in 1 g propylene carbonate (Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 5 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 15:50:15:20.

[0127] An automatic drawdown coater (Gardo automatic drawdown machine II) with a 6 MIL stainless steel bird bar (BYK-Gardner GmbH) was utilized to coat a 6 MIL wet film thickness onto a two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with tungsten oxide. This substrate had a Kapton tape “spacer” applied along two edges before the material was coated onto it.

[0128] A second two inch by two inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, nickel oxide in this case, was placed on top of on the coated film and was left to settle, which resulted in excess electrolyte seeping out the edges. The device was then placed in a 100 °C convection oven, for one (1) hour. The device was removed from the oven and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external PIB seal (Helioseal).

[0129] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 180 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 75% and the coloured state had a transmittance of 30%. Fig. 8 shows 120 switching cycles for the device.Example 8

[0130] In a first container, 15 g of polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was added to a 50 g plasticizer blend of dimethyl adipate and dimethyl-2-methyl glutarate (Solvay). The solution was stirred mechanically until the PVB was fully dissolved in the plasticizer blend. In a second container, 15 g of lithium bis(trifluoromethylsulfonyl)imide (Gelon) was dissolved in 20 g propylene carbonate (Sigma). The two solutions were combined and stirred at about 35 °C until a clear viscous formulation was obtained. This gave 100 g of electrolyte (ion-conducting) material with PVB: Plasticizer: Li salt:PC mass percent ratio of 15:50:15:20.

[0131] The formulation was applied onto a twelve inch by twelve inch piece of fluouro-silicone release liner and a second piece release liner was placed on top of the electrolyte formulation. The electrolyte was flattened within the two liners to create a uniform thickness film. The electrolyte material between the release liners was cooled to below room temperature, to decrease the tackiness of the material as well as its adhesion to the release liner. Once the material was appropriately cooled, the release liners were removed and the electrolyte film was placed onto a twelve inch by twelve inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with an anodic or cathodic electrochromic oxide film. In this case, the substrate had been coated with nickel oxide.

[0132] A second twelve inch by twelve inch piece of fluorine-doped tin oxide (FTO) coated glass (TEC 10; 10 Q / sq) (Pilkington, Toledo, OH, USA) that previously been coated with a complementary electrochromic oxide film, tungsten oxide in this case, was placed on top of on the ion-conducting PVB film. The device was then placed in a 100 °C convection oven, for one (1) hour. The device was removed from the oven and cooled to room temperature. Once at room temperature, no creep or slippage of the two substrates occurred. The exterior was cleaned, and the perimeter was sealed with an external polyisobutylene (PIB) seal (Helioseal).

[0133] The device was cycled between its coloured and bleached states by applying alternating consecutive bias voltages (-1 .5 V and +1 .5 V) to the device at 300 second intervals. The change in transmittance at CIE Y scale for the device as a function of time was recorded. The bleached state had a transmittance of 68% and the coloured state had a transmittance of 28%. Fig. 9 shows 78 switching cycles for the device.Example 9

[0134] In a container, plasticizer of diethylene glycol dibutyl ether (Sigma), lithium bis(trifluoromethylsulfonyl)imide (Gelon), and propylene carbonate (Sigma) were combined to obtain a solution. In a separate container, polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was heated to 50 °C for 48 h in vacuo. The PVB was added to the solution and stirred until all PVB particles appeared to be coated with the solution. This gave a substantially semi-solid or solid mixture with a PVB: Plasticizer: Li salt: PC mass percent ratio of 48:20:12:20. The mixture was pressed at 100 °C for 30 min, then cooled to 60 °C prior to the release of pressure to obtain an ion-conducting film. The conductivity of the ion-conducting film was measured at 1 .3 x 10'5(S cm-1).Example 10

[0135] In a container, plasticizer of diethylene glycol dibutyl ether (Sigma), lithium bis(trifluoromethylsulfonyl)imide (Gelon), and propylene carbonate (Sigma) were combined to obtain a solution. In a separate container, polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was heated to 50 °C for 48 h in vacuo. The PVB was added to the solution and stirred until all PVB particles appeared to be coated with the solution. This gave a substantially semi-solid or solid mixture with a PVB: Plasticizer: Li salt: PC mass percent ratio of 56:16:12:16. The mixture was pressed at 100 °C for 30 min, then cooled to 60 °C prior to the release of pressure to obtain an ion-conducting film. The conductivity of the ion-conducting film was measured at 7.2 x 10'6(S cm'1).Example 11

[0136] In a container, plasticizer of diethylene glycol dibutyl ether (Sigma), lithium bis(trifluoromethylsulfonyl)imide (Gelon), and propylene carbonate (Sigma) were combined to obtain a solution. In a separate container, polyvinyl butyral (PVB) resin (Mowital B 45 H, Kuraray) was heated to 50 °C for 48 h in vacuo. The PVB was added to the solution and stirred until all PVB particles appeared to be coated with the solution. This gave a substantially semi-solid or solid mixture with a PVB: Plasticizer: Li salt: PC mass percent ratio of 54:22.4:16:9.6. The mixture was pressed at 100 °C for 30 min, then cooled to 60 °C prior to the release of pressure toobtain an ion-conducting film. The conductivity of the ion-conducting film was measured at 3.9 x 10'6(S cm'1).

[0137] In the examples described herein, certain steps may be performed in a climate-controlled atmosphere, such as an atmosphere of less than about 1000 parts per million water. Certain steps may be performed in an inert atmosphere, such as an argon atmosphere. Furthermore, the mixture may be placed between pressing plates that are lined with a non-stick material such as polytetrafluoroethylene (PTFE) and sealed in a vacuum container, such as a vacuum bag, to reduce moisture contamination. Other variations of the examples will be apparent.

[0138] Fig. 10A is a flow diagram depicting a process 100 for forming an ionconducting material according to various embodiments. The process 100 includes a step 102 in which polyvinyl butyral (PVB) polymer resin and one or more plasticizers are combined to form a first combination. The one or more plasticizers include one or more oxygenated organic compounds that are liquid at about 20 °C.

[0139] In various embodiments, the PVB polymer resin includes from about 1 wt% to about 4 wt% of polyvinyl acetate, from about 11 wt% to about 21 wt% of polyvinyl alcohol, and from about 75 wt% to about 88 wt% of acetal. In some embodiments, the one or more oxygenated organic compounds include one or more of dimethyl glutarate, dimethyl 2-methylglutarate, dimethyl adipate, and diethylene glycol dibutyl ether.

[0140] In some embodiments, the one or more oxygenated organic compounds include one or more of di-n-butyl phthalate, diisononyl phthalate, bis(2-ethylhexyl) phthalate, di(2-ethylhexyl) adipate, diisodecyl adipate, tricresyl phosphate, acetyl tributyl citrate, tributyl citrate, polyester-based plasticizers, epoxidized soybean oil, diethylene glycol dibenzoate, and bio-based plasticizers (for example, castor oil derivatives). In various embodiments, the one or more plasticizers may include one or more of phthalate plasticizers, adipate plasticizers, phosphate plasticizers, citrate plasticizers, polyester plasticizers, epoxy plasticizers, and glycol ether-based plasticizers.

[0141] At a step 104 one or more lithium salts and one or more solvents are combined to form a second combination. The one or more solvents have a dielectricconstant greater than about four (4) and less than about 100 at about 20 °C. In various embodiments, the one or more lithium salts include one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate, and lithium difluoro(oxalato)borate. In some embodiments, the one or more solvents include one or more of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate.

[0142] At a step 106 the first combination and the second combination are combined to obtain a material. In various embodiments, the material includes from about 15 wt% to about 45 wt% of the PVB polymer resin, about 15 wt% to about 50 wt% of the one or more plasticizers, about 5 wt% to about 15 wt% of the one or more lithium salts, and about 15 wt% to about 35 wt% of the one or more solvents. In such embodiments, the material is a liquid material, forming the layer of the material includes forming a wet film of the liquid material, and exposing the layer to a temperature of about 75 °C to about 150 °C includes exposing the wet film to a temperature of about 75 °C to about 150 °C.

[0143] In some embodiments, the material includes from about 45 wt% to about 60 wt% of the PVB polymer resin, about 15 wt% to about 25 wt% of the one or more plasticizers, about 10 wt% to about 20 wt% of the one or more lithium salts, and about 5 wt% to about 25 wt% of the one or more solvents. In such embodiments, the material is a solid or semi-solid material, forming the layer of the material includes forming a layer of the solid or semi-solid material, and exposing the layer to a temperature of about 75 °C to about 150 °C includes exposing the layer of the solid or semi-solid material to a temperature of about 75 °C to about 150 °C.

[0144] According to certain embodiments, the material includes the one or more oxygenated organic compounds and the one or more solvents in a mass ratio of about 1 :1 , about 2.5:1 , about 5:1 , or about 1 :2. In some embodiments, the material further includes an additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof. The additive may be combined with the PVB polymer resin and the one or more plasticizers to form the first combination or maybe combined with the one or more lithium salts and the one or more solvents to form the second combination.

[0145] At a step 108 a layer of the material is formed. At a step 110 the layer is exposed to a temperature of about 75 °C to about 150 °C. The process 100 may be performed to form an ion-conducting material, such as an ion-conducting film. It will be understood that there may be other steps to a process for forming an ionconducting material that are not illustrated in Fig. 10A. An example step may be adding the additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof to the PVB polymer resin and the one or more plasticizers to form the first combination or to the one or more lithium salts and the one or more solvents to form the second combination. Other example steps include mixing the components of the first combination or the components of the second combination to form a substantially homogenous mixture, mixing the first combination and the second combination to form a substantially homogenous material, and allowing the one or more solvents to at least partially evaporate prior to exposing the layer of the material to the temperature of about 75 °C to about 150 °C.

[0146] Fig. 10B is a flow diagram depicting a process 120 for forming an ionconducting film according to various embodiments. The steps of the process 120 may be performed in conjunction with the steps of the process 100 of Fig. 10A. In various embodiments, the material of the process 100 of Fig. 10A is a liquid material and forming the layer of the material includes applying the liquid material onto a first release liner to form a wet film on the first release liner. The process 120 includes a step 122 in which a second release liner is placed such that the second release liner contacts the wet film. The process 120 also includes a step 124 in which pressure is applied to the wet film while exposing the wet film to a temperature of about 75 °C to about 150 °C to form an ion-conducting film between the first release liner and the second release liner. The process 120 may include additional steps not illustrated in Fig. 10B, such as a step of separating the ion-conducting film from the first release liner and the second release liner.

[0147] Fig. 10C is a flow diagram depicting a process 130 for forming an electrochromic device according to various embodiments. The steps of the process130 may be performed in conjunction with the steps of the process 100 of Fig. 10A. In some embodiments, the material of the process 100 of Fig. 10A is a liquid material and forming the layer of the material includes applying the liquid material onto a first electrochromic layer carried by a first transparent substrate to form a wet film on the first electrochromic layer. The process 130 includes a step 132 in which a second transparent substrate carrying a second electrochromic layer complementary to the first electrochromic layer is placed on the wet film such that the second electrochromic layer contacts the wet film. The process 130 also includes a step 134 in which the first transparent substrate, the first electrochromic layer, the wet film, the second electrochromic layer, and the second transparent substrate are exposed to the temperature of about 75 °C to about 150 °C to form an ion-conducting layer between the first electrochromic layer and the second electrochromic layer. The process 130 also includes a step 136 in which a seal is applied around a perimeter of the ion-conducting layer.

[0148] Fig. 11 is a flow diagram depicting a process 150 for forming an ionconducting film according to various embodiments. The process 150 includes a step 152 in which one or more plasticizers, one or more lithium salts, and one or more solvents are combined to obtain a solution. The one or more plasticizers include one or more oxygenated organic compounds that are liquid at about 20 °C. The one or more solvents have a dielectric constant greater than about four (4) and less than about 100 at about 20 °C.

[0149] In various embodiments, the one or more oxygenated organic compounds include one or more of dimethyl glutarate, dimethyl adipate, dimethyl-2-methyl glutarate, and diethylene glycol dibutyl ether. In some embodiments, the one or more lithium salts include one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate. In various embodiments, the one or more solvents include one or more of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate. In some embodiments, the solution includes the one or more plasticizers and the one or more solvents in a mass ratio of about 1 :1 or about 7:3.

[0150] In some embodiments, the one or more oxygenated organic compounds include one or more of di-n-butyl phthalate, diisononyl phthalate, bis(2-ethylhexyl) phthalate, di(2-ethylhexyl) adipate, diisodecyl adipate, tricresyl phosphate, acetyl tributyl citrate, tributyl citrate, polyester-based plasticizers, epoxidized soybean oil, diethylene glycol dibenzoate, and bio-based plasticizers (for example, castor oil derivatives). In various embodiments, the one or more plasticizers may include one or more of phthalate plasticizers, adipate plasticizers, phosphate plasticizers, citrate plasticizers, polyester plasticizers, epoxy plasticizers, and glycol ether-based plasticizers.

[0151] The process 150 also includes a step 154 in which polyvinyl butyral (PVB) polymer resin is exposed to a temperature of about 40 °C to about 60 °C (for example, about 50 °C). In various embodiments, the PVB polymer resin is exposed to the temperature of about 40 °C to about 60 °C for about 48 hours in a nearvacuum environment in order to reduce the humidity to which the PVB polymer resin is exposed. In some embodiments, the PVB polymer resin is exposed to the temperature of about 40 °C to about 60 °C in a climate-controlled atmosphere of less than about 1000 parts per million water.

[0152] In some embodiments, the PVB polymer resin includes from about 1 wt% to about 4 wt% of polyvinyl acetate, from about 11 wt% to about 21 wt% of polyvinyl alcohol, and from about 75 wt% to about 88 wt% of acetal.

[0153] The process 150 also includes a step 156 in which the solution and the PVB polymer resin are combined to form a mixture. In some embodiments, the solution and the PVB polymer resin are combined to form the mixture in a climate-controlled atmosphere of less than about 1000 parts per million water.

[0154] In various embodiments, the mixture includes from about 45 wt% to about 60 wt% of the PVB polymer resin, about 15 wt% to about 25 wt% of the one or more plasticizers, about 10 wt% to about 20 wt% of the one or more lithium salts, and about 5 wt% to about 25 wt% of the one or more solvents. In some embodiments, the mixture also includes an additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof.

[0155] The process 150 also includes a step 158 in which the mixture is melted and a step 160 in which an ion-conducting film of the mixture is formed. In various embodiments, the ion-conducting film of the mixture is formed by extruding the mixture to form the ion-conducting film. The process 150 may include additional steps not illustrated in Fig. 11 , such as a step of adding the additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof to the solution, combining the additive with the PVB polymer resin, or adding the additive to the mixture. Other additional steps that may be included in the process 150 include steps of feeding the solution and the PVB polymer resin into an extruder, heating the mixture in various temperature-controlled sections of the extruder to melt the mixture, and mixing the solution and the PVB polymer resin.

[0156] Fig. 12A is a schematic representation of a curved electrochromic device 170 that may be manufactured using PVB ion-conducting materials that are formed using processes in accordance with some embodiments. The curved electrochromic device 170 may be a curved electrochromic window such as a sunroof, a windshield, or a window for an automobile.

[0157] The curved electrochromic device 170 includes a first pane of conductive glass 171 and a second pane of conductive glass 177. The first pane of conductive glass 171 and the second pane of conductive glass 177 may be transparent conductive oxide (TCO) glass that is coated with a metal coating that makes the glass electrically conductive. The metal coating may include indium tin oxide (ITO) or fluorine-doped tin oxide (FTO). The curved electrochromic device 170 also includes an anodic electrochromic layer 173 and a cathodic electrochromic layer 175. The curved electrochromic device 170 also includes an ion-conducting layer 174, which may be referred to as an electrolyte layer or an interlayer, positioned between the anodic electrochromic layer 173 and the cathodic electrochromic layer 175. The ionconducting layer 174 may be formed according to embodiments of the processes described herein.

[0158] The curved electrochromic device 170 also includes a first seal 178a and a second seal 178b positioned around a perimeter of the ion-conducting layer 174, and a first bus bar 179a positioned proximate to the conductive glass 171 and a secondbus bar 179b positioned proximate to the conductive glass 177. The first seal 178a and the second seal 178b may function to prevent or reduce ingress of water or other contaminants. In certain embodiments of the curved electrochromic device 170, if no electrical bias is applied, ions (for example, lithium ions) are stored in the anodic electrochromic layer 173 and the curved electrochromic device 170 is in a transparent state. If an electrical bias is applied to the first bus bar 179a and the second bus bar 179b, ions (for example, lithium ions) migrate from the anodic electrochromic layer 173 across the ion-conducting layer 174 to be stored in the cathodic electrochromic layer 175, and the curved electrochromic device 170 transitions to a coloured state. The curved electrochromic device 170 may include other components not illustrated in Fig. 12A.

[0159] Fig. 12B is a schematic representation of a flat electrochromic device 180 that may be manufactured using PVB ion-conducting materials that are formed using processes in accordance with some embodiments. The flat electrochromic device180 may be an electrochromic window for a building such as a home or an office building.

[0160] The flat electrochromic device 180 includes a first pane of conductive glass181 and a second pane of conductive glass 187. The first pane of conductive glass 181 and the second pane of conductive glass 187 may be transparent conductive oxide (TCO) glass that is coated with a metal coating that makes the glass electrically conductive. The metal coating may include indium tin oxide (ITO) or fluorine-doped tin oxide (FTO). The flat electrochromic device 180 also includes an anodic electrochromic layer 183 and a cathodic electrochromic layer 185. The flat electrochromic device 180 also includes an ion-conducting layer 184, which may be referred to as an electrolyte layer or an interlayer, positioned between the anodic electrochromic layer 183 and the cathodic electrochromic layer 185. The ionconducting layer 184 may be formed according to embodiments of the processes described herein.

[0161] The flat electrochromic device 180 also includes a first seal 189 and a second seal 192. The first seal 189 and the second seal 192 may function to prevent or reduce ingress of water or other contaminants. The flat electrochromic device 180 also includes a third pane of glass 190 and a spacer 191 positioned between thesecond pane of conductive glass 187 and the third pane of glass 190. The spacer 191 may be aluminum or another suitable material. The flat electrochromic device 180 may include other components not illustrated in Fig. 12B.

[0162] In certain embodiments of the flat electrochromic device 180, if no electrical bias is applied, ions (for example, lithium ions) are stored in the anodic electrochromic layer 183 and the flat electrochromic device 180 is in a transparent state. If an electrical bias is applied to the flat electrochromic device 180, ions (for example, lithium ions) migrate from the anodic electrochromic layer 183 across the ion-conducting layer 184 to be stored in the cathodic electrochromic layer 185, and the flat electrochromic device 180 transitions to a coloured state.

[0163] The following are examples of processes, compositions, and devices according to various embodiments.

[0164] In some aspects, the techniques described herein relate to a process for forming an ion-conducting PVB film coated substrate for use in the manufacture of an electrochromic device, including the steps of: providing a first mixture including a PVB polymer resin and a plasticizer component including one or more methyl diester solvents; providing a second mixture including a lithium salt in a solvent component including one or more solvents having a high dielectric constant; combining and stirring the first mixture and the second mixture to provide a clear liquid ionconducting PVB material; applying the liquid ion-conducting PVB material to a substrate, wherein the substrate is a transparent substrate coated with a transparent conductive coating and an electrochromic metal oxide layer; and curing the coated substrate at a temperature of about 75 °C to about 150 °C at ambient pressure to form the ion-conducting PVB film coated substrate.

[0165] In some aspects, the techniques described herein relate to a process, wherein the step of applying includes extruding, pouring, painting, casting, or drawing down the liquid ion-conducting PVB material onto the substrate.

[0166] In some aspects, the techniques described herein relate to a process, wherein the step of applying is repeated until a desired thickness of the PVB film is achieved.

[0167] In some aspects, the techniques described herein relate to a process, wherein the coated transparent substrate is prepared using a process including the steps of: providing a transparent substrate having a conductive coating; spray coating the transparent substrate and conductive coating with a solution including one or more inorganic or organometallic precursors in a solvent; and exposing the one or more inorganic or organometallic precursors to at least one of IR radiation, UV radiation, ozone, or a combination thereof, to convert the one or more precursors to the electrochromic metal oxide layer.

[0168] In some aspects, the techniques described herein relate to a process, wherein the precursor is an inorganic chloride, an inorganic nitrate, an organometallic 2-ethylhexanoate, an organometallic butoxide, an organometallic ethoxide, an organometallic methoxide, an organometallic isopropoxide, an organometallic acetylacetonate, an organometallic silanolate, an organometallic oxalate, or mixtures thereof.

[0169] In some aspects, the techniques described herein relate to a process, wherein the solvent is selected from water, methanol, ethanol, isopropanol, acetone, hexane, acetylacetone, methyl isobutyl ketone, propylene glycol methyl ether acetate (PGMEA), ethyl acetate, acetonitrile, ethylene glycol, tetrahydrofuran (THF), toluene, and N-methylpyrrolidone and combinations thereof.

[0170] In some aspects, the techniques described herein relate to a process, wherein the transparent substrate is glass, plastic or a polymer.

[0171] In some aspects, the techniques described herein relate to a process, wherein the conductive coating includes fluorine tin oxide (FTO), indium tin oxide (ITO), aluminum zinc oxide (AZO), silver mesh, silver nanoparticles, carbon nanotubes, carbon black, graphene, conductive polymers, or any combination thereof.

[0172] In some aspects, the techniques described herein relate to a process, wherein the conductive coating is fluorine tin oxide (FTO) or indium tin oxide (ITO).

[0173] In some aspects, the techniques described herein relate to a process, wherein the electrochromic metal oxide layer is an anodic electrochromic metal oxide layer.

[0174] In some aspects, the techniques described herein relate to a process, wherein the anodic electrochromic layer includes NiOx, LiNiOx, NiNbOx, NiNbLiOx, NiAILiOx, VOx, or any combination thereof.

[0175] In some aspects, the techniques described herein relate to a process, wherein the anodic electrochromic metal oxide layer includes nickel oxide or doped nickel oxide.

[0176] In some aspects, the techniques described herein relate to a process, wherein the electrochromic metal oxide layer is a cathodic electrochromic metal oxide layer.

[0177] In some aspects, the techniques described herein relate to a process, wherein the cathodic electrochromic metal oxide layer includes WOx, WNbOx, TiWOx, LiWOx, or any combination thereof.

[0178] In some aspects, the techniques described herein relate to a process, wherein the cathodic electrochromic metal oxide layer includes tungsten oxide or doped tungsten oxide.

[0179] In some aspects, the techniques described herein relate to a process, wherein the electrochromic metal oxide layer includes a doped metal oxide including a dopant atom selected from niobium, aluminum, cerium, lithium, tantalum, molybdenum, cobalt and titanium.

[0180] In some aspects, the techniques described herein relate to a process, wherein the electrochromic metal oxide layer includes a metal oxide selected from the group consisting of NiOx, WOx, MoOx, TiOx, TaOx, VOx, NbOx, CoOx, IrOx, MnOx, FeOx, LiNiOx, WNbOx, TiWOx, LiWOx, NiNbOx, NiNbLiOx, NiAILiOx, and any combination thereof.

[0181] In some aspects, the techniques described herein relate to a process, wherein the process for preparing the coated transparent substrate further includesthe step of applying a barrier layer including niobium oxide, lithium oxide, titanium oxide, tantalum oxide, cerium oxide aluminum oxide, or a mixture thereof, wherein the barrier layer is applied onto the electrochromic metal oxide layer.

[0182] In some aspects, the techniques described herein relate to a process, wherein said barrier layer includes niobium oxide, lithium oxide or a combination thereof.

[0183] In some aspects, the techniques described herein relate to an ionconducting PVB film coated substrate prepared using the described processes.

[0184] In some aspects, the techniques described herein relate to a process for preparing an electrochromic device including the steps of: providing an ionconducting PVB film coated substrate; providing a transparent substrate coated with a conductive coating and an electrochromic metal oxide layer; and placing the ionconducting PVB film coated substrate and the transparent substrate in facial contact, wherein the ion-conducting PVB film is sandwiched between the coated substrates.

[0185] In some aspects, the techniques described herein relate to a process, wherein the ion-conducting PVB film coated substrate includes an anodic electrochromic metal oxide layer, and wherein the electrochromic metal oxide layer on the transparent substrate is a cathodic electrochromic metal oxide layer.

[0186] In some aspects, the techniques described herein relate to a process, wherein the ion-conducting PVB film coated substrate includes a cathodic electrochromic metal oxide layer, and wherein the electrochromic metal oxide layer on the transparent substrate is an anodic electrochromic metal oxide layer.

[0187] In some aspects, the techniques described herein relate to a process for forming an ion-conducting PVB film for use in the manufacture of an electrochromic device, including the steps of: providing a first mixture including a PVB polymer resin and a plasticizer component including one or more methyl diester solvents; providing a second mixture including a lithium salt in a solvent component including one or more solvents having a high dielectric constant; combining and stirring the first mixture and the second mixture and stirring to provide a clear liquid ion-conducting PVB material; forming a film from the liquid ion-conducting PVB material; and curingthe ion-conducting PVB film at a temperature of about 75 °C to about 150 °C at ambient pressure.

[0188] In some aspects, the techniques described herein relate to a process, wherein the step of forming the ion-conducting PVB film includes extruding, pouring, painting, casting, or drawing down the liquid ion-conducting PVB material to form a film layer.

[0189] In some aspects, the techniques described herein relate to a process, wherein the PVB film has a thickness of about 25 pm to about 2000 pm, preferably about 50 pm to about 1000 pm.

[0190] In some aspects, the techniques described herein relate to a process, wherein the PVB film is cured at a temperature of 80 °C for 2 hours at ambient pressure.

[0191] In some aspects, the techniques described herein relate to a process, wherein the PVB film is cured at a temperature of 100 °C for 1 hour at ambient pressure.

[0192] In some aspects, the techniques described herein relate to a process, wherein the PVB film is cured at a temperature of 130 °C for 30 min at ambient pressure.

[0193] In some aspects, the techniques described herein relate to a process, wherein the PVB film includes about 15 wt% to about 45 wt% PVB polymer resin, about 15 wt% to about 50 wt% plasticizer component, about 5 wt% to about 15 wt% lithium salt, and about 15 wt% to about 35 wt% solvent component.

[0194] In some aspects, the techniques described herein relate to a process, wherein the PVB polymer includes a polyvinyl acetate content of about 1 wt% to about 4 wt%, a polyvinyl alcohol content of about 11 wt% to about 21 wt%, and an acetal content of about 75 wt% to about 88 wt%.

[0195] In some aspects, the techniques described herein relate to a process, wherein the lithium salt is selected from lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithiumbis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate.

[0196] In some aspects, the techniques described herein relate to a process, wherein the methyl diester solvent is selected from dimethyl glutarate, dimethyl 2- methylglutarate, dimethyl adipate, and any combination thereof.

[0197] In some aspects, the techniques described herein relate to a process, wherein the high dielectric constant solvent is selected from propylene carbonate, tetraglyme, ethylene carbonate, and any combination thereof.

[0198] In some aspects, the techniques described herein relate to a process, wherein the PVB film includes the methyl diester solvent and the high dielectric constant solvent in a mass ratio of 1 :1 , 2.5:1 , 5:1 or 1 :2.

[0199] In some aspects, the techniques described herein relate to a process, wherein the PVB further includes an additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof.

[0200] In some aspects, the techniques described herein relate to a process, wherein the step of forming the ion-conducting PVB film includes: applying the liquid ion-conducting PVB material on to a substrate to form a coated substrate; and cooling the coated substrate to form an ion-conducting PVB film coated substrate.

[0201] In some aspects, the techniques described herein relate to a process, wherein the step of forming the ion-conducting PVB film includes: applying the liquid ion-conducting PVB material on to a release liner to form a coated release liner, cooling the coated release liner to form an ion-conducting PVB film coated release liner

[0202] In some aspects, the techniques described herein relate to a process, wherein the step of forming the ion-conducting PVB film includes: applying the liquid ion-conducting PVB material on to a first release liner to form a coated release liner,placing a second release liner on the coated side of the coated release liner, and cooling the assembly to form an ion-conducting PVB film between two release liners.

[0203] In some aspects, the techniques described herein relate to a process, wherein the step of applying is repeated until a desired thickness of the PVB film is achieved.

[0204] In some aspects, the techniques described herein relate to an ionconducting PVB film prepared using the described processes.

[0205] In some aspects, the techniques described herein relate to a process for preparing an electrochromic device including the steps of: providing an ionconducting PVB film; providing a first transparent substrate coated with a conductive coating and an anodic electrochromic metal oxide film; and providing a second transparent substrate coated with a conductive coating and a cathodic electrochromic metal oxide film; wherein the ion-conducting PVB film is sandwiched between the first coated transparent substrate and the second coated transparent substrate.

[0206] In some aspects, the techniques described herein relate to a process, wherein the electrochromic device is a flat electrochromic device.

[0207] In some aspects, the techniques described herein relate to a process, wherein the electrochromic device is a curved electrochromic device.

[0208] While specific examples are described above for illustrative purposes, various equivalent modifications are possible. For example, while processes or blocks are presented in a given order, alternative implementations may perform routines having steps, or employ systems having blocks, in a different order, and some processes or blocks may be deleted, moved, added, subdivided, combined, and / or modified to provide alternative or sub-combinations. Each of these processes or blocks may be implemented in a variety of different ways. Also, while processes or blocks are at times shown as being performed in series, these processes or blocks may instead be performed or implemented concurrently or in parallel or may be performed at different times. Further any specific numbers noted herein are only examples: alternative implementations may employ differing values or ranges.

[0209] Throughout this specification, plural instances may implement components, operations, or structures described as a single instance. Structures and functionality presented as separate components in example configurations may be implemented as a combined structure or component. Similarly, structures and functionality presented as a single component may be implemented as separate components. These and other variations, modifications, additions, and improvements fall within the scope of the subject matter herein. Furthermore, any specific numbers noted herein are only examples: alternative implementations may employ differing values or ranges.

[0210] Components may be described or illustrated as contained within or connected with other components. Such descriptions or illustrations are examples only, and other configurations may achieve the same or similar functionality. Components may be described or illustrated as “coupled,” “couplable,” “operably coupled,” “communicably coupled” and the like to other components. Such description or illustration should be understood as indicating that such components may cooperate or interact with each other, and may be in direct or indirect physical, electrical, or communicative contact with each other.

[0211] Components may be described or illustrated as “configured to,” “adapted to,” “operative to,” “configurable to,” “adaptable to,” “operable to” and the like. Such description or illustration should be understood to encompass components both in an active state and in an inactive or standby state unless required otherwise by context.

[0212] The use of “or” in this disclosure is not intended to be understood as an exclusive “or.” Rather, “or” is to be understood as including “and / or.” For example, the phrase “providing products or services” is intended to be understood as having several meanings: “providing products,” “providing services,” and “providing products and services.”

[0213] It may be apparent that various modifications may be made, and other embodiments may be used without departing from the broader scope of the discussion herein. For example, although an electrochromic window is described as being in a transparent state in the absence of an electrical bias, the electrochromic window may be in a coloured state in the absence of an electrical bias. Therefore,these and other variations upon the example embodiments are intended to be covered by the disclosure herein. Furthermore, PVB ion-conducting materials as described herein may have applicability as electrolytes or interlayers in devices such as batteries, fuel cells, electrolyzers for hydrogen production, supercapacitors, organic light-emitting diodes (OLEDs), or photovoltaics.

Claims

CLAIMSI / We claim:1 . A process comprising: combining polyvinyl butyral (PVB) polymer resin and one or more plasticizers to form a first combination, the one or more plasticizers including one or more oxygenated organic compounds that are liquid at about 20 °C; combining one or more lithium salts and one or more solvents to form a second combination, the one or more solvents having a dielectric constant greater than about four (4) and less than about 100 at about 20 °C; combining the first combination and the second combination to obtain a material; forming a layer of the material; and exposing the layer to a temperature of about 75 °C to about 150 °C.

2. The process of claim 1 wherein the material includes from about 15 wt% to about 45 wt% of the PVB polymer resin, about 15 wt% to about 50 wt% of the one or more plasticizers, about 5 wt% to about 15 wt% of the one or more lithium salts, and about 15 wt% to about 35 wt% of the one or more solvents, the material is a liquid material, forming the layer of the material includes forming a wet film of the liquid material, and exposing the layer to a temperature of about 75 °C to about 150 °C includes exposing the wet film to a temperature of about 75 °C to about 150 °C.

3. The process of claim 1 wherein the material includes from about 45 wt% to about 60 wt% of the PVB polymer resin, about 15 wt% to about 25 wt% of the one or more plasticizers, about 10 wt% to about 20 wt% of the one or more lithium salts, and about 5 wt% to about 25 wt% of the one or more solvents, the material is a solid or semi-solid material, forming the layer of the material includes forming a layer of the solid or semi-solid material, and exposing the layer to a temperature of about75 °C to about 150 °C includes exposing the layer of the solid or semi-solid material to a temperature of about 75 °C to about 150 °C.

4. The process of claim 1 wherein the PVB polymer resin includes from about 1 wt% to about 4 wt% of polyvinyl acetate, from about 11 wt% to about 21 wt% of polyvinyl alcohol, and from about 75 wt% to about 88 wt% of acetal.

5. The process of claim 1 wherein the one or more oxygenated organic compounds include one or more of dimethyl glutarate, dimethyl 2-methylglutarate, dimethyl adipate, and diethylene glycol dibutyl ether.

6. The process of claim 1 wherein the one or more lithium salts include one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate, and lithium difluoro(oxalato)borate.

7. The process of claim 1 wherein the one or more solvents include one or more of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate.

8. The process of claim 1 wherein the material includes the one or more oxygenated organic compounds and the one or more solvents in a mass ratio of about 1 :1 , about 2.5:1 , about 5:1 , or about 1 :2.

9. The process of claim 1 wherein the material further includes an additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers, radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof.

10. The process of claim 1 wherein the material is a liquid material, forming the layer of the material includes applying the liquid material onto a first release liner to form a wet film on the first release liner, and the process further comprises: placing a second release liner such that the second release liner contacts the wet film; andapplying pressure to the wet film while exposing the wet film to a temperature of about 75 °C to about 150 °C to form an ion-conducting film between the first release liner and the second release liner.11 .An ion-conducting material formed according to the process of any of claims 1 to 10.

12. An electrochromic device manufactured using an ion-conducting material formed according to the process of any of claims 1 to 10.

13. The process of claim 1 wherein the material is a liquid material, forming the layer of the material includes applying the liquid material onto a first electrochromic layer carried by a first transparent substrate to form a wet film on the first electrochromic layer, and the process further comprises: placing a second transparent substrate carrying a second electrochromic layer complementary to the first electrochromic layer on the wet film such that the second electrochromic layer contacts the wet film; exposing the first transparent substrate, the first electrochromic layer, the wet film, the second electrochromic layer, and the second transparent substrate to the temperature of about 75 °C to about 150 °C to form an ion-conducting layer between the first electrochromic layer and the second electrochromic layer; and applying a seal around a perimeter of the ion-conducting layer.

14. An electrochromic device formed according to the process of claim 13.

15. A process comprising: combining one or more plasticizers, one or more lithium salts, and one or more solvents to obtain a solution, the one or more plasticizers including one or more oxygenated organic compounds that are liquid at about 20 °C, the one or more solvents having a dielectric constant greater than about four (4) and less than about 100 at about 20 °C; exposing polyvinyl butyral (PVB) polymer resin to a temperature of about 40 °C to about 60 °C;combining the solution and the PVB polymer resin to form a mixture; melting the mixture; and forming an ion-conducting film of the mixture.

16. The process of claim 15 wherein combining the solution and the PVB polymer resin to form the mixture includes combining the solution and the PVB polymer resin to form the mixture in an atmosphere of less than about 1000 parts per million water.

17. The process of claim 15 wherein the mixture includes from about 45 wt% to about 60 wt% of the PVB polymer resin, about 15 wt% to about 25 wt% of the one or more plasticizers, about 10 wt% to about 20 wt% of the one or more lithium salts, and about 5 wt% to about 25 wt% of the one or more solvents.

18. The process of claim 15 wherein the PVB polymer resin includes from about 1 wt% to about 4 wt% of polyvinyl acetate, from about 11 wt% to about 21 wt% of polyvinyl alcohol, and from about 75 wt% to about 88 wt% of acetal.

19. The process of claim 15 wherein the one or more oxygenated organic compounds include one or more of dimethyl glutarate, dimethyl adipate, dimethyl-2- methyl glutarate, and diethylene glycol dibutyl ether.

20. The process of claim 15 wherein the one or more lithium salts include one or more of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(oxalato)borate and lithium difluoro(oxalato)borate.

21. The process of claim 15 wherein the one or more solvents include one or more of propylene carbonate, sulfolane, tetraglyme, and ethylene carbonate.

22. The process of claim 15 wherein the mixture includes the one or more plasticizers and the one or more solvents in a mass ratio of about 1 :1 or about 7:3.

23. The process of claim 15 wherein the mixture further includes an additive selected from fillers, ultraviolet stabilizers, heat stabilizers, adhesion improvers,radical scavengers, antioxidants, ultraviolet light absorber, or any combination thereof.

24. The process of claim 15 wherein forming an ion-conducting film of the mixture includes extruding the mixture to form the ion-conducting film.

25. An ion-conducting film formed according to the process of any of claims 15 to 24.

26. An electrochromic device manufactured using an ion-conducting film formed according to the process of any of claims 15 to 24.

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