Heat-strengthenable or temperable electrochromic electrodes, and associated processes and manufactures

Abstract

Electrochromic electrodes capable of withstanding temperatures sufficient for tempering or heat strengthening and remaining functional. An example electrochromic electrode includes a glass substrate that has not been heat- strengthened or tempered, an electrically conductive layer, an electrochromic layer including one or more metal oxides, and one or more of: (1) a base layer between the electrically conductive layer and the electrochromic layer, (2) a capping layer on the electrochromic layer, and (3) one or more dopants included in the electrochromic layer. The electrochromic electrode may be heat-strengthened or tempered and maintain specified functionality. The electrochromic electrodes may be utilized in electrochromic devices such as electrochromic windows or other electrochemical devices.

Description

HEAT-STRENGTHENABLE OR TEMPERABLE ELECTROCHROMIC ELECTRODES, AND ASSOCIATED PROCESSES AND MANUFACTURESTECHNICAL FIELD

[0001] The present disclosure relates in general to electrodes, and in particular to electrochromic electrodes that may be heat-strengthened or tempered.BACKGROUND

[0002] In the glass industry, coated glass (for example, low emissivity coated glass) is manufactured by a relatively small number of glass manufacturers in a small number of large stock sizes. The stock size coated glass is then cut and tempered or heat-strengthened by a relatively larger number of glass fabricators. By limiting the number of stock sizes of coated glass that are manufactured, glass manufacturers may achieve significant efficiencies of scale, thereby reducing cost and lead-times for end consumers.

[0003] Electrochromic films currently used in electrochromic windows do not survive sufficiently high temperatures for tempering or heat-strengthening the glass substrate after the electrochromic film is applied. As such, unlike with other types of coated glass, it is common for the relatively small number of glass manufacturers to make electrochromic electrodes to size for final consumers. Alternatively, glass fabricators may undesirably invest large amounts of capital in their own electrochromic coating infrastructure so that cutting of the substrate can be done inhouse followed by tempering or heat-strengthening and then coating with the electrochromic film. In either case, the efficiencies of scale that are seen for manufacturing other types of coated glass (for example, low emissivity coated glass) are not achieved in manufacturing electrochromic windows, thereby resulting in higher complexity, higher costs, lower quality and longer lead-times for customers seeking electrochromic windows.

[0004] No admission is necessarily intended, nor should be construed, that any of the preceding information constitutes prior art.SUMMARY

[0005] In some aspects, the techniques described herein relate to a process for manufacturing an electrochromic electrode, the process including: forming an electrically conductive layer on a glass substrate, wherein the glass substrate is not heat-strengthened or tempered; applying a solution on a layer on the glass substrate, wherein the solution includes one or more metal-containing precursors to be converted into one or more metal oxides; converting the one or more metalcontaining precursors into the one or more metal oxides to form an electrochromic layer on the layer, wherein the electrochromic layer includes the one or more metal oxides; and performing one or more of: prior to applying the solution on the layer, forming a base layer on the electrically conductive layer, wherein the base layer includes first material, and applying the solution on the layer includes applying the solution on the base layer; forming a capping layer on the electrochromic layer, wherein the capping layer includes second material; and applying one or more dopants on the layer with the one or more metal-containing precursors.

[0006] In some aspects, the techniques described herein relate to a process wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes exposing the one or more metal-containing precursors to one or more of ultraviolet radiation, infrared radiation, and ozone to form the electrochromic layer on the layer.

[0007] In some aspects, the techniques described herein relate to a process wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes exposing the one or more metal-containing precursors to one or more temperatures of approximately 150 °C to approximately 650 °C to form the electrochromic layer on the layer.

[0008] In some aspects, the techniques described herein relate to a process wherein exposing the one or more metal-containing precursors to the one or more temperatures of approximately 150 °C to approximately 650 °C to form the electrochromic layer on the layer is a first exposure that is performed prior to forming the capping layer on the electrochromic layer, the one or more temperatures are one or more first temperatures, and the capping layer on the electrochromic layer is formed by a second exposure to one or more second temperatures of approximately 150 °C to approximately 650 °C.

[0009] In some aspects, the techniques described herein relate to a process, further including annealing at least the electrochromic layer.

[0010] In some aspects, the techniques described herein relate to a process wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes converting the one or more metal-containing precursors into one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx to form an anodic electrochromic layer on the layer.

[0011] In some aspects, the techniques described herein relate to a process wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes converting the one or more metal-containing precursors into one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx to form a cathodic electrochromic layer on the layer.

[0012] In some aspects, the techniques described herein relate to a process wherein the solution further includes one or more templating agents or one or more lithium salts.

[0013] In some aspects, the techniques described herein relate to a process wherein the first material includes one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.

[0014] In some aspects, the techniques described herein relate to a process wherein the second material includes one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

[0015] In some aspects, the techniques described herein relate to a process wherein the one or more metal oxides are different from both the first material and the second material.

[0016] In some aspects, the techniques described herein relate to a process wherein the one or more dopants include one or more metal or metalloid oxide dopants, and one or more metals or metalloids of the one or more metal or metalloidoxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium or one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

[0017] In some aspects, the techniques described herein relate to a process wherein a ratio of the one or more metal or metalloid oxide dopants to the one or more metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more metal or metalloid oxide dopants per mol. of the one or more metal oxides.

[0018] In some aspects, the techniques described herein relate to a process wherein the one or more dopants are one or more first dopants, and the process further includes including one or more second dopants in one or more of the base layer and the capping layer.

[0019] In some aspects, the techniques described herein relate to a process wherein the electrically conductive layer has a first coefficient of thermal expansion, the electrochromic layer has a second coefficient of thermal expansion, and the base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

[0020] In some aspects, the techniques described herein relate to an electrochromic electrode including: a glass substrate, the glass substrate not heat- strengthened or tempered; an electrically conductive layer; an electrochromic layer including one or more metal oxides; and one or more of: a base layer between the electrically conductive layer and the electrochromic layer, the base layer including first material; a capping layer on the electrochromic layer, the capping layer including second material; and one or more dopants included in the electrochromic layer.

[0021] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrochromic layer is an anodicelectrochromic layer and the one or more metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx.

[0022] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrochromic layer is a cathodic electrochromic layer and the one or more metal oxides include one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx.

[0023] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the first material includes one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.

[0024] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the second material includes one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

[0025] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the one or more metal oxides are different from both the first material and the second material.

[0026] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the one or more dopants include one or more metal or metalloid oxide dopants, and one or more metals or metalloids of the one or more metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium or one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

[0027] In some aspects, the techniques described herein relate to an electrochromic electrode wherein a ratio of the one or more metal or metalloid oxidedopants to the one or more metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more metal or metalloid oxide dopants per mol. of the one or more metal oxides.

[0028] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrically conductive layer has a first coefficient of thermal expansion, the electrochromic layer has a second coefficient of thermal expansion, and the base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

[0029] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrochromic electrode is capable of withstanding heat-strengthening or tempering at one or more temperatures between approximately 600 °C and approximately 700 °C while maintaining a specified charge capacity.

[0030] In some aspects, the techniques described herein relate to a process including: cutting a first electrochromic electrode to first dimensions, the first electrochromic electrode including: a first glass substrate; a first electrically conductive layer; a first electrochromic layer including one or more first metal oxides; and one or more of: a first base layer between the first electrically conductive layer and the first electrochromic layer, the first base layer including first material; a first capping layer on the first electrochromic layer, the first capping layer including second material; and one or more first dopants included in the first electrochromic layer; heat-strengthening or tempering the first electrochromic electrode to form a first heat-strengthened or tempered electrochromic electrode; cutting a second electrochromic electrode to second dimensions, the second electrochromic electrode complementary to the first electrochromic electrode, the second electrochromic electrode including: a second glass substrate; a second electrically conductive layer; a second electrochromic layer including one or more second metal oxides; and one or more of: a second base layer between the second electrically conductive layer and the second electrochromic layer, the second base layer including third material; a second capping layer on the second electrochromic layer, the second capping layer including fourth material; and one or more second dopants included in thesecond electrochromic layer; and heat-strengthening or tempering the second electrochromic electrode to form a second heat-strengthened or tempered electrochromic electrode.

[0031] In some aspects, the techniques described herein relate to a process wherein the one or more first metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx, and the first electrochromic layer is an anodic electrochromic layer.

[0032] In some aspects, the techniques described herein relate to a process wherein the one or more second metal oxides include or one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx, and the second electrochromic layer is a cathodic electrochromic layer.

[0033] In some aspects, the techniques described herein relate to a process wherein both the first material and the third material include one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.

[0034] In some aspects, the techniques described herein relate to a process wherein both the second material and the fourth material include one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

[0035] In some aspects, the techniques described herein relate to a process wherein the one or more first metal oxides are different from both the first material and the second material, and the one or more second metal oxides are different from both the third material and the fourth material.

[0036] In some aspects, the techniques described herein relate to a process wherein the one or more first dopants include one or more first metal or metalloid oxide dopants, and one or more first metals or metalloids of the one or more first metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony,selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium, and the one or more second dopants include one or more second metal or metalloid oxide dopants, and one or more second metals or metalloids of the one or more second metal or metalloid oxide dopants are one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

[0037] In some aspects, the techniques described herein relate to a process wherein a first ratio of the one or more first dopants to the one or more first metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more first dopants per mol. of the one or more first metal oxides, and a second ratio of the one or more second dopants to the one or more second metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more second dopants per mol. of the one or more second metal oxides.

[0038] In some aspects, the techniques described herein relate to a process wherein the first electrically conductive layer has a first coefficient of thermal expansion, the first electrochromic layer has a second coefficient of thermal expansion, and the first base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

[0039] In some aspects, the techniques described herein relate to a process, further including: positioning an electrolyte between the first heat-strengthened or tempered electrochromic electrode and the second heat-strengthened or tempered electrochromic electrode; coupling one or more first electrical connectors to the first heat-strengthened or tempered electrochromic electrode; coupling one or more second electrical connectors to the second heat-strengthened or tempered electrochromic electrode; and sealing the electrolyte between the first heat- strengthened or tempered electrochromic electrode and the second heat- strengthened or tempered electrochromic electrode.

[0040] In some aspects, the techniques described herein relate to an electrochromic device including: a first heat-strengthened or tempered electrochromic electrode including: a first glass substrate; a first electricallyconductive layer; a first electrochromic layer including one or more first metal oxides; and at least one of: a first base layer between the first electrically conductive layer and the first electrochromic layer, the first base layer including first material; a first capping layer on the first electrochromic layer, the first capping layer including second material; and one or more first dopants included in the first electrochromic layer; a second heat-strengthened or tempered electrochromic electrode, the second heat-strengthened or tempered electrochromic electrode complementary to the first heat-strengthened or tempered electrochromic electrode, the second heat- strengthened or tempered electrochromic electrode including: a second glass substrate; a second electrically conductive layer; a second electrochromic layer including one or more second metal oxides; and at least one of: a second base layer between the second electrically conductive layer and the second electrochromic layer, the second base layer including third material; a second capping layer on the second electrochromic layer, the second capping layer including fourth material; and one or more second dopants included in the second electrochromic layer; and an electrolyte between the first heat-strengthened or tempered electrochromic electrode and the second heat-strengthened or tempered electrochromic electrode, wherein the first electrically conductive layer, the first electrochromic layer, and at least one of the first base layer and the first capping layer were formed on the first glass substrate prior to heat-strengthening or tempering the first glass substrate to form the first heat-strengthened or tempered electrochromic electrode, and the second electrically conductive layer, the second electrochromic layer, and at least one of the second base layer and the second capping layer were formed on the second glass substrate prior to heat-strengthening or tempering the second glass substrate to form the second heat-strengthened or tempered electrochromic electrode.

[0041] In some aspects, the techniques described herein relate to an electrochromic device wherein the first electrochromic layer is an anodic electrochromic layer and the one or more first metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx.

[0042] In some aspects, the techniques described herein relate to an electrochromic device wherein the second electrochromic layer is a cathodicelectrochromic layer and the one or more second metal oxides include or one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx.

[0043] In some aspects, the techniques described herein relate to an electrochromic device wherein both the first material and the third material include one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.

[0044] In some aspects, the techniques described herein relate to an electrochromic device wherein both the second material and the fourth material include one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

[0045] In some aspects, the techniques described herein relate to an electrochromic device wherein the one or more first metal oxides are different from both the first material and the second material, and the one or more second metal oxides are different from both the third material and the fourth material.

[0046] In some aspects, the techniques described herein relate to an electrochromic device wherein the one or more first dopants include one or more first metal or metalloid oxide dopants, and one or more first metals or metalloids of the one or more first metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium, and the one or more second dopants include one or more second metal or metalloid oxide dopants, and one or more second metals or metalloids of the one or more second metal or metalloid oxide dopants are one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

[0047] In some aspects, the techniques described herein relate to an electrochromic device wherein a first ratio of the one or more first dopants to the oneor more first metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more first dopants per mol. of the one or more first metal oxides, and a second ratio of the one or more second dopants to the one or more second metal oxides is between approximately 0.005 and approximately 1.0 mol. of the one or more second dopants per mol. of the one or more second metal oxides.

[0048] In some aspects, the techniques described herein relate to an electrochromic device wherein the first electrically conductive layer has a first coefficient of thermal expansion, the first electrochromic layer has a second coefficient of thermal expansion, and the first base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive.

[0050] Fig. 1 A is a schematic depiction of a heat-strengthenable or temperable anodic electrochromic electrode according to some embodiments.

[0051] Fig. 1 B is a schematic depiction of a heat-strengthenable or temperable cathodic electrochromic electrode according to some embodiments.

[0052] Fig. 2 depicts a method of manufacturing an electrochromic device according to some embodiments.

[0053] Figs. 3A to 3D depict aspects of the method of manufacturing an electrochromic device of Fig. 2 according to some embodiments.

[0054] Fig. 4A is a schematic representation of a curved electrochromic device according to various embodiments.

[0055] Fig. 4B is a schematic representation of a flat electrochromic device according to various embodiments.

[0056] Throughout the drawings, like reference numerals will be understood to refer to like parts, components, and structures.DETAILED DESCRIPTION

[0057] Electrochromic coatings and electrochromic electrodes that can withstand high temperatures such as those experienced when thermally tempering or heatstrengthening glass and still provide specified functionality would have significant utility.

[0058] The present disclosure describes electrochromic electrodes capable of withstanding temperatures sufficient for tempering or heat strengthening and remaining functional over their lifespans. Such electrochromic electrodes include a glass substrate, an electrically conductive layer, an electrochromic layer, and one or more of: (1 ) a base layer between the electrically conductive layer and the electrochromic layer, (2) a capping layer on the electrochromic layer, and (3) one or more dopants included in the electrochromic layer. The electrochromic electrodes may be heat-strengthened or tempered. Additional processing steps may be performed before, during, or after the heat-strengthening or tempering, such as cutting the electrochromic electrodes to required dimensions and bending the electrochromic electrodes. The electrochromic electrodes may be utilized in electrochromic devices such as electrochromic windows or other electrochemical devices.

[0059] The electrochromic electrodes described herein may be manufactured by glass manufacturers in the same or similar sizes as panes of float glass. Therefore, one advantage of the described technology is that the glass manufacturers may keep inventory of the electrochromic electrodes and provide the electrochromic electrodes to glass fabricators, who can then cut the electrochromic electrodes to appropriate sizes and heat-strengthen or temper the electrochromic electrodes. Another advantage is that glass manufacturers may already have the necessary equipment, processes, and expertise to implement the described technology without undue difficulty, and thus glass fabricators may be spared from having to devote significant resources to set up manufacturing of electrochromic electrodes. Accordingly, manufacturing of electrochromic electrodes may be simplified orstreamlined by utilization of the disclosed technology, thereby reducing costs or increasing productivity. Furthermore, manufacturing of electrochromic devices that include the described electrochromic electrodes may also be improved.

[0060] Fig. 1A is a schematic depiction of an anodic electrochromic electrode 100 according to some embodiments, and Fig. 1 B is a schematic depiction of a cathodic electrochromic electrode 120 according to some embodiments. Each of the anodic electrochromic electrode 100 (which may be referred to as an anode or an anodic electrode) and the cathodic electrochromic electrode 120 (which may be referred to as a cathode or a cathodic electrode) may be subjected to heat-strengthening or tempering and still provide specified functionality (for example, charge capacity). Furthermore, each of the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 may still allow for electrochromic devices that include the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 to provide specified functionality (for example, visual light transmittance or switching time). Aspects of the layers of the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120, including the thicknesses, the shapes, the sizes, and the scales of the layers, are not necessarily drawn to scale or in actual proportions, but are represented schematically for illustrative purposes.

[0061] In various embodiments, one or both of the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 may not fully meet specified functionality prior to being heat-strengthened or tempered. The anodic electrochromic electrode 100 or the cathodic electrochromic electrode 120 may become fully functional after heat-strengthening or tempering or other processes.

[0062] The anodic electrochromic electrode 100 includes a glass substrate 102, an electrically conductive layer 104, and an anodic electrochromic layer 108. The anodic electrochromic electrode 100 also includes a base layer 106 between the electrically conductive layer 104 and the anodic electrochromic layer 108 and a capping layer 110 on the anodic electrochromic layer 108. The anodic electrochromic electrode 100 may also include one or more dopants (not illustrated in Fig. 1A) in the anodic electrochromic layer 108. The cathodic electrochromic electrode 120 includes a glass substrate 122, an electrically conductive layer 124, and a cathodic electrochromic layer 128. The cathodic electrochromic electrode 120also includes a base layer 126 between the electrically conductive layer 124 and the cathodic electrochromic layer 128 and a capping layer 130 on the cathodic electrochromic layer 128. The cathodic electrochromic electrode 120 may also include one or more dopants (not illustrated in Fig. 1 B) in the cathodic electrochromic layer 128.

[0063] Fig. 1A depicts the anodic electrochromic electrode 100 as including the base layer 106 and the capping layer 110. However, an anodic electrochromic electrode according to various embodiments does not include either the base layer 106, the capping layer 110, or both. For example, an anodic electrochromic electrode may include the base layer 106 but not the capping layer 110 and may or may not include the one or more dopants in the anodic electrochromic layer 108. As another example, an anodic electrochromic electrode may include the capping layer 110 but not the base layer 106 and may or may not include the one or more dopants in the anodic electrochromic layer 108. As another example, an anodic electrochromic electrode may include neither the capping layer 110 nor the base layer 106 but include one or more dopants in the anodic electrochromic layer 108.

[0064] Similarly, Fig. 1 B depicts the cathodic electrochromic electrode 120 as including the base layer 126 and the capping layer 130. However, a cathodic electrochromic electrode according to various embodiments does not include either the base layer 126, the capping layer 130, or both. For example, a cathodic electrochromic electrode may include the base layer 126 but not the capping layer 130 and may or may not include the one or more dopants in the cathodic electrochromic layer 128. As another example, a cathodic electrochromic electrode may include the capping layer 130 but not the base layer 126 and may or may not include the one or more dopants in the cathodic electrochromic layer 128. As another example, a cathodic electrochromic electrode may include neither the capping layer 130 nor the base layer 126 but include one or more dopants in the cathodic electrochromic layer 128.

[0065] Each of the glass substrate 102 and the glass substrate 122 may be or include any suitable glass substrate. In some embodiments, each of the glass substrate 102 and the glass substrate 122 is transparent or substantially transparent. In some embodiments, each of the glass substrate 102 and the glass substrate 122is translucent. In various embodiments, each of the glass substrate 102 and the glass substrate 122 is a pane of float glass.

[0066] Each of the electrically conductive layer 104 and the electrically conductive layer 124 may be or include electrically conductive material, such as transparent electrically conductive material. For example, each of the electrically conductive layer 104 and the electrically conductive layer 124 may be or include a transparent conductive oxide (TCO). The transparent conductive oxide may be or include indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum zinc oxide (AZO), or other suitable material. Each of the electrically conductive layer 104 and the electrically conductive layer 124 may thus be transparent or substantially transparent. In some embodiments, each of the electrically conductive layer 104 and the electrically conductive layer 124 is translucent. Each of the electrically conductive layer 104 and the electrically conductive layer 124 may be electrically conductive and conduct charge to and from the anodic electrochromic layer 108 and the cathodic electrochromic layer 128, respectively (for example, to and from an external power source or control electronics).

[0067] Each of the base layer 106 and the base layer 126 may be or include transparent material. Each of the base layer 106 and the base layer 126 may thus be transparent or substantially transparent. In some embodiments, each of the base layer 106 and the base layer 126 is translucent. Each of the base layer 106 and the base layer 126 may have a thickness (for example, a minimum dimension) of between approximately 5 nanometers (nm) and 500nm, such as between approximately 5nm and 300nm or between approximately 5nm and 200nm.

[0068] In various embodiments, each of the base layer 106 and the base layer 126 includes material that is different from the material of the anodic electrochromic layer 108 or the cathodic electrochromic layer 128, respectively. That is, the material of the base layer 106 has a different composition than the material of the anodic electrochromic layer 108 and the material of the base layer 126 has a different composition than the material of the cathodic electrochromic layer 128. In various embodiments, one or both of the base layer 106 and the base layer 126 includes one or more of titanium oxide (TiOx), cerium oxide (CeOx), zirconium oxide (ZrOx), cerium-titanium oxide (CeTiOx), indium oxide (InOx), ITO, silicon oxide (SiOx),tungsten oxide (WOx), copper oxide (CuOx) and tin oxide (SnOx). One or both of the base layer 106 and the base layer 126 may include nanoparticles of any of the foregoing oxides. For example, one or both of the base layer 106 and the base layer 126 may include TiOx nanoparticles, CeOx nanoparticles, or ITO nanoparticles.

[0069] In some embodiments, one or both of the base layer 106 and the base layer 126 includes one or more of TiOx, CeOx, ZrOx, CeTiOx and InOx. One or both of the base layer 106 and the base layer 126 may include nanoparticles of any of the foregoing oxides. For example, one or both of the base layer 106 and the base layer 126 may include TiOx nanoparticles or CeOx nanoparticles.

[0070] In various embodiments, one or both of the base layer 106 and the base layer 126 includes one or more of TiOx, CeOx, CeTiOx and InOx. One or both of the base layer 106 and the base layer 126 may include nanoparticles of any of the foregoing oxides. For example, one or both of the base layer 106 and the base layer 126 may include TiOx nanoparticles.

[0071] The composition of the base layer 106 may be dependent on a composition of the electrically conductive layer 104 or a composition of the anodic electrochromic layer 108. For example, the composition of the base layer 106 may be dependent on a coefficient of thermal expansion (CTE) of the electrically conductive layer 104 and a CTE of the anodic electrochromic layer 108. In such examples, the composition of the base layer 106 may be chosen such that the CTE of the base layer 106 is between the CTE of the electrically conductive layer 104 and the CTE of the anodic electrochromic layer 108. For example, where the electrically conductive layer 104 includes FTO having a CTE of approximately 3.5x1 O’6K1and the anodic electrochromic layer 108 includes nickel oxide (NiOx) having a CTE of approximately 13x1 O’6K’1, the base layer 106 may include, for example, TiO2 having a CTE of between approximately 8.4x1 O’6K1and 11 .8x1 O’6K’1.

[0072] Similarly, the composition of the base layer 126 may be dependent on a composition of the electrically conductive layer 124 or a composition of the cathodic electrochromic layer 128. For example, the composition of the base layer 126 may be dependent on a coefficient of thermal expansion (CTE) of the electrically conductive layer 124 and a CTE of the cathodic electrochromic layer 128. In suchexamples, the composition of the base layer 126 may be chosen such that the CTE of the base layer 126 is between the CTE of the electrically conductive layer 124 and the CTE of the cathodic electrochromic layer 128.

[0073] The base layer 106 may (on its own or in conjunction with one or more of the capping layer 110 and the one or more dopants in the anodic electrochromic layer 108) allow the anodic electrochromic electrode 100 to be heat-strengthened or tempered and still function as an anodic electrochromic electrode. Similarly, the base layer 126 may on its own or in conjunction with one or more of the capping layer 130 and the one or more dopants in the cathodic electrochromic layer 128) allow the cathodic electrochromic electrode 120 to be heat-strengthened or tempered and still function as a cathodic electrochromic electrode. The base layer 106 may assist in conducting charge to and from the anodic electrochromic layer 108. Similarly, the base layer 126 may assist in conducting charge to and from the cathodic electrochromic layer 128.

[0074] For the anodic electrochromic electrode 100, the anodic electrochromic layer 108 may be on the electrically conductive layer 104 or on the base layer 106. In some embodiments, the anodic electrochromic layer 108 is transparent or substantially transparent. In some embodiments, the anodic electrochromic layer 108 is translucent. The anodic electrochromic layer 108 may have a thickness (for example, a minimum dimension) of between approximately 100nm and approximately 2000nm, such as between approximately 300nm and approximately 1500nm or between approximately 400nm and approximately 1300nm.

[0075] The anodic electrochromic layer 108 may be or include any suitable electrochromic material that can withstand a heat-strengthening or tempering of the anodic electrochromic electrode 100 at one or more temperatures between approximately 600 °C and approximately 700 °C (for example, at approximately 640 °C).

[0076] In some embodiments, the anodic electrochromic layer 108 includes one or more metal oxides. Where the anodic electrochromic layer 108 includes two or more metal oxides, the anodic electrochromic layer 108 may be described as including mixed metal oxides. The one or more metal oxides may include one or more of NiOx,lithium-nickel oxide (LiNiOx), nickel-niobium oxide (NiNbOx), nickel-silicon-lithium oxide (NiSiLiOx), nickel-silicon-magnesium-lithium oxide (NiSiMgLiOx), nickel- niobium-lithium oxide (NiNbLiOx), nickel-aluminum-lithium oxide (NiAILiOx), cobalt oxide (CoOx), iridium oxide (IrOx), manganese oxide (MnOx), iron oxide (FeOx), vanadium oxide (VOx), CeOx and CeTiOx. In some embodiments, the one or more metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx and NiNbLiOx. In some embodiments, the one or more metal oxides include one or more of NiSiLiOx, NiSiMgLiOx and NiNbLiOx.

[0077] Including one or more of CeOx and CeOx in the anodic electrochromic layer 108 may increase a charge capacity of the anodic electrochromic electrode 100 after the anodic electrochromic electrode 100 has been heat-strengthened or tempered electrode. Increasing the charge capacity of the anodic electrochromic electrode 100 may increase durability for electrochromic devices incorporating the anodic electrochromic electrode 100 by providing a reservoir of extra charge during cycling.

[0078] In some embodiments the one or more metal oxides include NiSiMgLiOx. In some embodiments, the one or more metal oxides include NiSiMgLiOx having a molar ratio of Ni: Si: Mg: Li of a:b:c:d, where a is between approximately 80 and approximately 120, b is between approximately 8 and approximately 12, c is between approximately 4 and approximately 6 and d is between approximately 24 and approximately 36. In some embodiments, the one or more metal oxides include NiSiMgLiOx with a molar ratio of Ni:Si: Mg: Li of 100:10:5:30. In some embodiments, the one or more metal oxides include NiSiMgLiOx and the ratio of silicon relative to nickel may be approximately 0.1 mol. silicon per mol. of nickel. In some embodiments, the one or more metal oxides include NiSiMgLiOx and the ratio of magnesium relative to nickel may be approximately 0.05 mol. magnesium per mol. of nickel. In some embodiments, the one or more metal oxides in the anodic electrochromic layer 108 include NiSiMgLiOx and the ratio of lithium relative to nickel may be approximately 0.3 mol. lithium per mol. of nickel.

[0079] In some embodiments, where the one or more metal oxides include nickel and lithium, a ratio of lithium relative to nickel may be approximately 0.01 to approximately 3.0 mol. lithium per mol. of nickel, or the ratio of lithium relative to the nickel may be approximately 0.1 to approximately 2.0 mol. lithium per mol. of nickel.In some embodiments, where the one or more metal oxides in the anodic electrochromic layer 108 include an additional element (for example, silicon, aluminum, niobium etc.) in addition to the nickel and lithium, the additional element may be present in a ratio of approximately 0.05 to approximately 1.0 mol. additional element per mol. of nickel or in a ratio of approximately 0.05 to approximately 0.5 mol. additional element per mol. of nickel.

[0080] In some embodiments, where the one or more metal oxides include NiSiLiOx, the ratio of lithium relative to nickel may be between approximately 0.01 to approximately 1 .0 mol. lithium per mol. of nickel, the ratio of lithium relative to nickel may be between approximately 0.01 to approximately 0.6 mol. lithium per mol. of nickel, the ratio of lithium relative to nickel may be between approximately 0.01 to approximately 0.4 mol. lithium per mol. of nickel, or the ratio of lithium relative to nickel may be between approximately 0.05 to approximately 0.4 mol. lithium per mol. of nickel. In some embodiments, where the one or more metal oxides include NiSiLiOx, the ratio of silicon relative to nickel may be between approximately 0.01 to approximately 3.0 mol. silicon per mol. of nickel, the ratio of silicon relative to nickel may be between approximately 0.05 to approximately 0.5 mol. silicon per mol. of nickel, the ratio of silicon relative to nickel may be between approximately 0.05 to approximately 0.4 mol. silicon per mol. of nickel, or the ratio of silicon relative to nickel may be between approximately 0.05 to approximately 0.2 mol. silicon per mol. of nickel.

[0081] In some embodiments, where the one or more metal oxides include NiNbLiOx, the ratio of lithium relative to nickel may be between approximately 0.5 to approximately 2.0 mol. lithium per mol. of nickel or the ratio of lithium relative to nickel may be between approximately 1 .0 to approximately 2.0 mol. lithium per mol. of nickel. In some embodiments, where the one or more metal oxides include NiNbLiOx, the ratio of niobium relative to nickel may be between approximately 0.01 to approximately 1 .0 mol. niobium per mol. of nickel, the ratio of niobium relative to nickel may be between approximately 0.05 to approximately 0.8 mol. niobium per mol. of nickel, or the ratio of niobium relative to nickel may be between approximately 0.1 to approximately 0.6 mol. silicon per mol. of nickel.

[0082] In some embodiments, where the one or more metal oxides include NiSiMgLiOx, the ratio of nickel relative to silicon, magnesium and lithium may be between approximately 1 .5 to approximately 2.0 mol. of silicon, magnesium and lithium per mol. nickel and the ratio of silicon relative to magnesium may be between approximately 0.5 to approximately 4.0 mol. silicon per mol. magnesium. In some embodiments, where the one or more metal oxides include NiSiMgLiOx, the ratio of nickel relative to silicon, magnesium and lithium may be between approximately 0.75 to approximately 2.0 mol. of silicon, magnesium and lithium per mol. nickel and the ratio of silicon relative to magnesium may be between approximately 1 .0 to approximately 3.0 mol. silicon per mol. magnesium. In some embodiments, where the one or more metal oxides include NiSiMgLiOx, the ratio of nickel relative to silicon, magnesium and lithium may be approximately 0.45 mol. of silicon, magnesium and lithium per mol. nickel and the ratio of silicon relative to magnesium may be approximately 2.0 mol. silicon per mol. magnesium.

[0083] The anodic electrochromic layer 108 may also include one or more templating agents such as, for example, a difunctional block copolymer surfactant (for example, PLURONIC™ P123), a nonionic surfactant (for example, TRITON™ X- 100), a nonionic, surfactant polyol (for example, PLURONIC™ F127), a polyether compound (for example, polyethylene glycol (PEG)), or a polymer compound (for example, polyvinylpyrrolidone (PVP)). Such templating agents may increase an ionic conductivity of the anodic electrochromic layer 108. For example, such templating agents may increase porosity of the anodic electrochromic layer 108 thereby improving lithium ion diffusion through the anodic electrochromic layer 108. The anodic electrochromic layer 108 may also include one or more lithium salts.

[0084] In some embodiments, the anodic electrochromic layer 108 also includes one or more dopants. In some embodiments, the one or more dopants include one or more metal or metalloid oxide dopants. The one or more metals or metalloids of the one or more metal or metalloid oxide dopants may be one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, andzirconium. The one or more dopants may include nanoparticles that include any of the foregoing (for example, titanium oxide nanoparticles).

[0085] In some embodiments, the anodic electrochromic layer 108 includes one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, or NiNbLiOx and one or more metal or metalloid oxide dopants. The one or more metals or metalloids of the one or more metal or metalloid oxide dopants may be one or more of cerium, aluminum, tantalum, molybdenum, titanium, indium, magnesium, yttrium, boron, fluorine, gallium, germanium, hafnium, lanthanum, sodium, phosphorus, antimony, selenium, vanadium, tungsten, zinc, and zirconium.

[0086] In some embodiments, the anodic electrochromic layer 108 includes one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, or NiNbLiOx and one or more metal or metalloid oxide dopants. The one or more metals or metalloids of the one or more metal or metalloid oxide dopants may be one or more of cerium, aluminum, tantalum, molybdenum, titanium, indium, magnesium, yttrium, boron, fluorine, gallium, germanium, lanthanum, sodium, phosphorus, vanadium, tungsten, zinc, and zirconium.

[0087] In various embodiments, a ratio of the one or more dopants portion of the anodic electrochromic layer 108 to the non-one or more dopants portion of the anodic electrochromic layer 108 (for example, the one or more metal oxides portion) may be approximately 0.005 to approximately 1 .0 mol. one or more dopants portion per mol non-one or more dopants portion. In some embodiments, a ratio of the one or more dopants portion of the anodic electrochromic layer 108 to the non-one or more dopants portion of the anodic electrochromic layer 108 may be approximately 0.005 to approximately 0.5 mol. one or more dopants portion per mol non-one or more dopants portion. In various embodiments, a ratio of the one or more dopants portion of the anodic electrochromic layer 108 to the non-one or more dopants portion of the anodic electrochromic layer 108 may be approximately 0.005 to approximately 0.4 mol. one or more dopants portion per mol non-one or more dopants portion. In some embodiments, a ratio of the one or more dopants portion of the anodic electrochromic layer 108 to the non-one or more dopants portion of the anodic electrochromic layer 108 may be approximately 0.005 to approximately 0.2 mol. one or more dopants portion per mol non-one or more dopants portion.

[0088] In embodiments where the anodic electrochromic layer 108 includes nickel (for example, a nickel oxide such as NiOx), a ratio of the one or more dopants portion of the anodic electrochromic layer 108 to the nickel portion of the anodic electrochromic layer 108 (for example, the NiOx portion) may be approximately 0.005 to approximately 1 .0 mol. one or more dopants portion per mol nickel portion, approximately 0.005 to approximately 0.5 mol. one or more dopants portion per mol. of nickel portion, approximately 0.005 to approximately 0.4 mol. one or more dopants portion per mol. of nickel portion, or approximately 0.005 to approximately 0.2 mol. one or more dopants portion per mol. of nickel portion.

[0089] For the cathodic electrochromic electrode 120, the cathodic electrochromic layer 128 may be on the electrically conductive layer 124 or on the base layer 126. In some embodiments, the cathodic electrochromic layer 128 is transparent or substantially transparent. In some embodiments, the cathodic electrochromic layer 128 is translucent. The cathodic electrochromic layer 128 may have a thickness (for example, a minimum dimension) of between approximately 100nm and approximately 1500nm, between approximately 200nm and approximately 1000nm or between approximately 200nm and approximately 600nm.

[0090] The cathodic electrochromic layer 128 may be or include any suitable electrochromic material that can withstand a heat-strengthening or tempering of the cathodic electrochromic electrode 120 at one or more temperatures between approximately 600 °C and approximately 700 °C (for example, at approximately 640 °C).

[0091] In some embodiments, the cathodic electrochromic layer 128 includes one or more metal oxides that are different from and complementary to the one or more metal oxides of the anodic electrochromic layer 108. The cathodic electrochromic layer 128 may be complementary to the anodic electrochromic layer 108. For example, the cathodic electrochromic layer 128 may color (for example, low transmittance of light) with ion insertion (intercalation) whereas the anodic electrochromic layer 108 may color with ion extraction (deintercalation).

[0092] Where the cathodic electrochromic layer 128 includes two or more metal oxides, the cathodic electrochromic layer 128 may be described as including mixedmetal oxides. The one or more metal oxides may include one or more of WOx, tungsten-niobium oxide (WNbOx), titanium-tungsten oxide (TiWOx), lithium-tungsten oxide (LiWOx), tungsten-lithium-aluminum oxide (WLiAIOx), tungsten-silicon-lithium oxide (WSiLiOx), tungsten-niobium-lithium oxide ( WNbLiOx), tungsten-niobium- lithium-silicon oxide (WNbLiSiOx), tungsten-niobium-aluminum oxide (WNbAIOx), molybdenum oxide (MoOx), TiOx, tanatalum oxide (TaOx), and niobium oxide (NbOx). In some embodiments, the one or more metal oxides include one or more of WLiAIOx, WSiLiOx, WNbLiOx, and WNbLiSiOx. In some embodiments, the one or more metal oxides include one or more of WLiAIOx, WSiLiOx, and WNbLiOx.

[0093] In some embodiments, where the one or more metal oxides includes tungsten and lithium, a ratio of lithium relative to tungsten may be approximately 0.05 to approximately 1.0 mol. lithium per mol. of tungsten, approximately 0.1 to approximately 0.7 mol. lithium per mol. of tungsten, or approximately 0.1 to approximately 0.5 mol. lithium per mol. of tungsten. In some embodiments, where the one or more metal oxides in the cathodic electrochromic layer 128 includes an additional element (for example, silicon, aluminum, etc.) in addition to the tungsten and lithium, the additional element may be present in a ratio of approximately 0.01 to approximately 1.0 mol. additional element per mol. of tungsten, in a ratio of approximately 0.05 to approximately 0.7 mol. additional element per mol. of tungsten, in a ratio of approximately 0.05 to approximately 0.5 mol. additional element per mol. of tungsten, or in a ratio of approximately 0.1 to approximately 0.5 mol. additional element per mol. of tungsten.

[0094] The cathodic electrochromic layer 128 may also include one or more templating agents such as, for example, a difunctional block copolymer surfactant (for example, PLURONIC™ P123), a nonionic surfactant (for example, TRITON™ X- 100), a nonionic, surfactant polyol (for example, PLURONIC™ F127), a polyether compound (for example, polyethylene glycol (PEG)), or a polymer compound (for example, polyvinylpyrrolidone (PVP)). Such templating agents may increase an ionic conductivity of the cathodic electrochromic layer 128. For example, such templating agents may increase porosity of the cathodic electrochromic layer 128 thereby improving lithium ion diffusion through the cathodic electrochromic layer 128. The cathodic electrochromic layer 128 may also include one or more lithium salts.

[0095] In some embodiments, the cathodic electrochromic layer 128 also includes one or more dopants. In some embodiments, the one or more dopants include one or more metal or metalloid oxide dopants. The one or more metals or metalloids of the one or more metal or metalloid oxide dopants may be one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium. In some embodiments, the one or more metals or metalloids of the one or more metal or metalloid oxide dopants are one of silicon, aluminum, niobium, lithium, cerium, magnesium, manganese, titanium, and nickel. In some embodiments, the one or more metals or metalloids of the one or more metal or metalloid oxide dopants are one of silicon, aluminum, niobium, lithium and magnesium. The one or more dopants may include nanoparticles that include any of the foregoing (for example, titanium oxide nanoparticles).

[0096] In various embodiments, a ratio of the one or more dopants portion of the cathodic electrochromic layer 128 to the non-one or more dopants portion of the cathodic electrochromic layer 128 (for example, the one or more metal oxides portion) may be approximately 0.005 to approximately 1 .0 mol. one or more dopants portion per mol. non-one or more dopants portion. In some embodiments, a ratio of the one or more dopants portion of the cathodic electrochromic layer 128 to the non- one or more dopants portion of the cathodic electrochromic layer 128 may be approximately 0.005 to approximately 0.7 mol. one or more dopants portion per mol. non-one or more dopants portion. In some embodiments, a ratio of the one or more dopants portion of the cathodic electrochromic layer 128 to the non-one or more dopants portion of the cathodic electrochromic layer 128 may be approximately 0.005 to approximately 0.5 mol. one or more dopants portion per mol. non-one or more dopants portion.

[0097] For the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120, each of the capping layer 110 and the capping layer 130 may be or include transparent material. Each of the capping layer 110 and the capping layer 130 may thus be transparent or substantially transparent. In some embodiments, each of the capping layer 110 and the capping layer 130 is translucent. Each of the capping layer 110 and the capping layer 130 may have a thickness (for example, a minimum dimension) of between approximately 50nm and500nm, such as between approximately 50nm and 400nm or between approximately 50nm and 300nm.

[0098] In various embodiments, each of the capping layer 110 and the capping layer 130 includes material that is different from the material of the anodic electrochromic layer 108 or the cathodic electrochromic layer 128, respectively. That is, the material of the capping layer 110 has a different composition than the material of the anodic electrochromic layer 108 and the material of the capping layer 130 has a different composition than the material of the cathodic electrochromic layer 128. In some embodiments, one or both of the capping layer 110 and the capping layer 130 includes one or more of aluminum oxide (AIOx), ZrOx, zinc oxide (ZnOx), SiOx, boron oxide (BOx such as B2O3), magnesium oxide (MgOx), niobium oxide (NbOx), CeOx, and CeTiOx. In various embodiments, one or both of the capping layer 110 and the capping layer 130 includes one or more of ZrOx, ZnOx, MgOx, NbOx, CeOx and CeTiOx. One or both of the capping layer 110 and the capping layer 130 may include nanoparticles of any of the foregoing oxides.

[0099] The capping layer 110 may (on its own or in conjunction with one or more of the base layer 106 and the one or more dopants in the anodic electrochromic layer 108) allow the anodic electrochromic electrode 100 to be heat-strengthened or tempered and still function as an anodic electrochromic electrode. Similarly, the capping layer 130 may (on its own or in conjunction with one or more of the base layer 126 and the one or more dopants in the cathodic electrochromic layer 128) allow the cathodic electrochromic electrode 120 to be heat-strengthened or tempered and still function as a cathodic electrochromic electrode.

[0100] The capping layer 110 may separate the anodic electrochromic layer 108 from an electrolyte (not shown in Fig. 1A) in an electrochromic device that includes the capping layer 110, which may in turn reduce degradation of the anodic electrochromic layer 108 or protect the electrolyte from the anodic electrochromic layer 108. Similarly, the capping layer 130 may separate the cathodic electrochromic layer 128 from the electrolyte (not shown in Fig. 1 B) in an electrochromic device that includes the cathodic electrochromic electrode 120, which may in turn reduce degradation of the cathodic electrochromic layer 128 or protect the electrolyte from the cathodic electrochromic layer 128.

[0101] The capping layer 110 may also increase adhesion between the anodic electrochromic electrode 100 and an electrolyte after the anodic electrochromic electrode 100 has been heat-strengthened or tempered. Such increase in adhesion may occur, for example, as the difference in a CTE of the capping layer 110 and a CTE of the electrolyte may be less than the difference in a CTE of the anodic electrochromic layer 108 and the CTE of the electrolyte. Furthermore, if the anodic electrochromic electrode 100 is exposed to a light source after the anodic electrochromic electrode 100 has been heat-strengthened or tempered and incorporated into an electrochromic device, the capping layer 110 may also serve to reduce an amount of ultraviolet radiation received by the anodic electrochromic layer 108. Such reduction may reduce or eliminate undesirable darkening of the electrochromic device.

[0102] Similarly, the capping layer 130 may also increase adhesion between the cathodic electrochromic electrode 120 and an electrolyte after the cathodic electrochromic electrode 120 has been heat-strengthened or tempered. Such increase in adhesion may occur, for example, as the difference in a CTE of the capping layer 130 and a CTE of the electrolyte may be less than the difference in a CTE of the cathodic electrochromic layer 128 and the CTE of the electrolyte. Furthermore, if the cathodic electrochromic electrode 120 is exposed to a light source after the cathodic electrochromic electrode 120 has been heat-strengthened or tempered and incorporated into an electrochromic device, the capping layer 130 may also serve to reduce an amount of ultraviolet radiation received by the cathodic electrochromic layer 128. Such reduction may reduce or eliminate undesirable darkening of the electrochromic device.

[0103] One or more of the base layer 106, the capping layer 110, and the one or more dopants in the anodic electrochromic layer 108 may allow the anodic electrochromic electrode 100 to be heat-strengthened or tempered and still maintain a specified functionality, such as a specified charge capacity. Similarly, one or more of the base layer 126, the capping layer 130, and the one or more dopants in the cathodic electrochromic layer 128 may allow the cathodic electrochromic electrode 120 to be heat-strengthened or tempered and still maintain a specified functionality, such as a specified charge capacity. In contrast, technology other than thatdescribed herein requires a substrate to be heat-strengthened or tempered before forming an electrochromic layer (or other layers) on the substrate to form an electrochromic electrode.

[0104] In various embodiments, one or both of the base layer 106 and the capping layer 110 may include one or more dopants, such as one or more metal or metalloid oxide dopants. Similarly, one or both of the base layer 126 and the capping layer 130 may include one or more dopants, such as one or more metal or metalloid oxide dopants. The one or more metals or metalloids of the one or more metal or metalloid oxide dopants in the base layer 106, the capping layer 110, the base layer 126, or the capping layer 130 may be one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, nickel, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium. The one or more dopants may include nanoparticles that include any of the foregoing.

[0105] In various embodiments, for one or more layers of the anodic electrochromic electrode 100 or the cathodic electrochromic electrode 120 to include one or more dopants, precursors to the one or more dopants (one or more dopant precursors) may be utilized. The one or more dopant precursors may convert or be converted to the one or more dopants (for example, by one or more exposures to elevated temperatures, ultraviolet radiation, near infrared radiation, ozone, plasma or annealing). Depending on the context, the term dopant should be interpreted to include a dopant precursor, and the term one or more dopants should be interpreted to include one or more dopant precursors.

[0106] Fig. 2 depicts a method 200 of manufacturing an electrochromic device according to some embodiments. The method 200 may start with step 202-1 or step 202-2. In some embodiments, a step with a reference character ending in “-2” may be generally similar to the corresponding step with a reference character ending in 1”. For example, step 202-2 corresponds to step 202-1 and may be generally similar to step 202-1 . In various embodiments, a step having a reference character ending in “-1” occurs in parallel (for example, concurrently or with at least some temporal overlap) with the step having a corresponding reference character ending in “-2”. Forexample, step 210-1 may occur in parallel with step 210-2. However, corresponding steps may occur in series. Moreover, steps may occur in orders other than what is illustrated in Fig. 2. The steps with reference characters ending in “-1” are now described

[0107] At step 202-1 a first electrically conductive layer is formed on a first glass substrate which is not heat-strengthened or tempered. Fig. 3A depicts an exemplary embodiment of the step 202-1 . The forming of a first electrically conductive layer 304 may utilize any suitable method, such as by one or more of spraying (for example, spray pyrolysis), spray coating, sputtering (for example, magnetron sputtering), thermal evaporation, pulsed laser deposition, curtain coating, slot die coating, gravure coating, roll to roll coating, dip coating, spin coating, inkjet printing, doctor blade, and screen printing. In some embodiments, the first electrically conductive layer 304 may be partially formed on the first glass substrate by spray coating, such as is depicted in Fig. 3A. Fig. 3A depicts particles 354 of the material for the first electrically conductive layer 304 may be deposited onto the first glass substrate 302. As the particles 354 are deposited on the first glass substrate 302, the thickness of the first electrically conductive layer 304 increases until a specified thickness, ti , is achieved. As can be seen from Fig. 3A, a surface 364 of the first electrically conductive layer 304 may not be perfectly planar due to the distribution of the particles 354.

[0108] In some embodiments, precursors of the material for the first electrically conductive layer 304 are deposited on the first glass substrate 302. For example, a precursor solution may be deposited on the first glass substrate 302. The precursors may convert or be converted into the material for the first electrically conductive layer 304. One or more further processing steps (not illustrated in Fig. 2 or Fig. 3A) (for example, one or more exposures to elevated temperatures, ultraviolet radiation, near infrared radiation, ozone, plasma or annealing) may be performed to complete formation of the first electrically conductive layer 304.

[0109] The method 200 may continue to step 204-1 where an optional first base layer may be formed on the first electrically conductive layer 304. For electrochromic electrodes where the first base layer is not present, step 204-1 may be skipped. Fig. 3B depicts an exemplary embodiment of the step 204-1. The forming of a first baselayer 306 may utilize any suitable method, such as by one or more of spraying (for example, spray pyrolysis), spray coating, sputtering (for example, magnetron sputtering), thermal evaporation, pulsed laser deposition, curtain coating, slot die coating, gravure coating, roll to roll coating, dip coating, spin coating, inkjet printing, doctor blade, and screen printing. In some embodiments, the first base layer 306 may be at least partially formed on the first electrically conductive layer 304 by spray coating, such as is depicted in Fig. 3B. Fig. 3B depicts that particles 356 of the material for the first base layer 306 may be deposited onto the first electrically conductive layer 304. In embodiments where the first base layer 306 includes a combination of compounds (for example, a combination of TiOx and CeOx), the compounds may be mixed before being applied or as they are being applied. As the particles 356 are deposited on the first electrically conductive layer 304, the thickness of the first base layer 306 increases until a specified thickness, t2, is achieved. As can be seen from Fig. 3B, a surface 366 of the first base layer 306 may not be perfectly planar due to the distribution of the particles 356.

[0110] In some embodiments, precursors of the material for the first base layer 306 are deposited on the first electrically conductive layer 304. For example, a precursor solution may be deposited on the first electrically conductive layer 304. The precursors may convert or be converted into the material for the first base layer 306. One or more further processing steps (not illustrated in Fig. 2 or Fig. 3B) (for example, one or more exposures to elevated temperatures, ultraviolet radiation, near infrared radiation, ozone, plasma or annealing) may be performed to complete formation of the first base layer 306.

[0111] The method 200 may continue to step 206-1 where a first solution that includes one or more first metal-containing precursors is applied to a layer on the glass substrate, which may be the first base layer 306 or the first electrically conductive layer 304 if step 204-1 was skipped. Step 206-1 may utilize any suitable method, such as by one or more of spraying (for example, spray pyrolysis), spray coating, sputtering (for example, magnetron sputtering), thermal evaporation, pulsed laser deposition, curtain coating, slot die coating, gravure coating, roll to roll coating, dip coating, spin coating, inkjet printing, doctor blade, and screen printing. In some embodiments, the first electrochromic layer may be partially formed on the layer byspray coating, such as is depicted in Fig. 3C. Fig. 3C depicts particles 358 of the first solution may be deposited onto the first base layer 306 (or the first electrically conductive layer 304 if the step 204-1 was skipped) to at least partially form a first electrochromic layer 308. In embodiments where the first electrochromic layer 308 includes a combination of compounds (for example, a combination of NiOx and CeOx), the compounds may be combined in the first solution before the first solution is applied (for example, before step 206-1 ) or as the first solution is applied. As the particles 358 are deposited onto the first base layer 306 (or the first electrically conductive layer 304 if the step 204-1 was skipped), the thickness of the first electrochromic layer 308 increases until a specified thickness, ts, is achieved. As can be seen from Fig. 3C, a surface 368 of the first electrochromic layer 308 may not be perfectly planar due to the distribution of the particles 358.

[0112] In embodiments where the first electrochromic layer 308 includes one or more dopants, the one or more dopants may be combined in the first solution with the one or more metal-containing precursors or as the first solution is applied. Additionally or alternatively, the one or more dopants may be applied with the solution (for example, by a separate deposition of the one or more dopants).

[0113] The method 200 may continue to step 210-1 where an optional first capping layer may be formed on the first electrochromic layer 308. For electrochromic electrodes where the first capping layer 310 is not present, step 210-1 may be skipped. The forming of the first capping layer 310 may utilize any suitable method, such as by one or more of spraying (for example, spray pyrolysis), spray coating, sputtering (for example, magnetron sputtering), thermal evaporation, pulsed laser deposition, curtain coating, slot die coating, gravure coating, roll to roll coating, dip coating, spin coating, inkjet printing, doctor blade, and screen printing. In some embodiments, the first capping layer 310 may be at least partially formed on the first electrochromic layer 308 by spray coating, such as is depicted in Fig. 3D. Fig. 3D depicts particles 360 of the material for the first capping layer 310 may be deposited onto the first electrochromic layer 308. In embodiments where the first capping layer 310 includes a combination of compounds (for example, a combination of ZrOx and MgOx), the compounds may be mixed before being applied or as they are being applied. As the particles 360 are deposited on the first electrochromic layer 308, thethickness of the first capping layer 310 increases until a specified thickness, t4, is achieved. As can be seen from Fig. 3D, a surface 370 of the first capping layer 310 may not be perfectly planar due to the distribution of the particles 360.

[0114] In some embodiments, precursors of the material for the first capping layer 310 are deposited on the first electrochromic layer 308. For example, a precursor solution may be deposited on the first electrochromic layer 308. The precursors may convert or be converted into the material for the first capping layer 310. One or more further processing steps (not illustrated in Fig. 2 or Fig. 3D) (for example, one or more exposures to elevated temperatures, ultraviolet radiation, near infrared radiation, ozone, plasma or annealing) may be performed to complete formation of the first capping layer 310.

[0115] Step 202-1 through step 208-1 may occur, for example, in a space or chamber with temperatures between approximately 15°C and approximately 30 °C. Step 202-1 through step 208-1 may occur, for example, in a space or chamber with a relative humidity of between approximately 15% and 25%.

[0116] The method 200 may continue to step 210-1 where the one or more metalcontaining precursors applied on the first electrically conductive layer 304 or the first base layer 306 are converted into one or more metal oxides to form at least partially the first electrochromic layer 308. The one or more metal-containing precursors may be converted into the one or more metal oxides using one or more of ultraviolet radiation, near infrared radiation, ozone, and plasma. 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 generating metal oxides and mixed-metal oxides using ultraviolet radiation, near infrared radiation, ozone, or a combination thereof. PCT Application No. PCT / CA2024 / 051712, filed December 20, 2024, and titled “PROCESSES FOR PREPARING METAL OXIDE LAYERS OR ION-CONDUCTIVE LAYERS UTILIZING PLASMA, AND ASSOCIATED MATERIALS AND DEVICES,” describes techniques for preparing metal oxide layers utilizing plasma. The entireties of U.S. Patent Publication No. US20200165161A1 and PCT Application No. PCT / CA2024 / 051712 are incorporated herein by reference in jurisdictions allowing such incorporation. The exposure of the one or more metal-containing precursors to one or more ofultraviolet radiation, near infrared radiation, ozone, and plasma may convert the one or more metal-containing precursors into the one or more metal oxides.

[0117] In various embodiments, in addition to or as an alternative to using one or more of ultraviolet radiation, near infrared radiation, ozone, and plasma, the one or more metal-containing precursors may be converted into the one or more metal oxides by exposing the one or more metal-containing precursors to elevated temperatures one or more times, such as temperatures between approximately 150 °C and approximately 650 °C, such as between approximately 300 °C and approximately 550 °C, between approximately 375 °C and approximately 475 °C, or between approximately 400 °C and approximately 450 °C. In some embodiments, the one or more metal-containing precursors may be exposed to elevated temperatures for between approximately 10 minutes and approximately 90 minutes, such as between approximately 20 minutes and approximately 60 minutes. In some embodiments, the relative humidity during the one or more exposures to elevated temperatures is less than approximately 25%. In some embodiments, fresh gas (for example, air) is flowed around or over the first electrochromic layer 308 or the first capping layer 310 to improve removal of byproducts.

[0118] In some embodiments, the use of one or more of ultraviolet radiation, near infrared radiation, ozone, plasma, and elevated temperatures at step 210-1 may also convert precursors in the first base layer 306 to the final material of the first base layer 306. For example, the first base layer 306 may include one or more metalcontaining or metalloid-containing precursors that are converted into one or more metal oxides or metalloid oxides. Similarly, the use of one or more of ultraviolet radiation, near infrared radiation, ozone, plasma, and elevated temperatures at step 210-1 may also convert precursors in the first capping layer 310 to the final material of the first capping layer 310. For example, the first capping layer 310 may include one or more metal-containing or metalloid-containing precursors that are converted into one or more metal oxides or metalloid oxides.

[0119] In various embodiments, each of the step 206-1 and the step 210-1 may be repeated. For example, a first application of the first solution including the one or more first metal-containing precursors to the layer may be made. Then, the one or more first metal-containing precursors of the first application may be converted intothe one or more metal oxides by a first exposure to one or more of ultraviolet radiation, near infrared radiation, ozone, plasma, and elevated temperatures. A second application of the first solution may be made. Then, the one or more first metal-containing precursors of the second application may be converted into the one or more metal oxides by a second exposure to one or more of ultraviolet radiation, near infrared radiation, ozone, plasma, and elevated temperatures. Step 206-1 and step 210-1 may be repeated until the specified thickness, ts, is achieved for the first electrochromic layer 308. Other variations will be apparent.

[0120] The method 200 continues at step 212-1 where at least the first electrochromic layer 308 is annealed at one or more temperatures between approximately 250 °C and approximately 500 °C. In some embodiments, annealing is performed at a temperature of approximately 400 °C. Annealing may take between approximately 5 minutes and approximately 120 minutes. In some embodiments, annealing takes between approximately 10 minutes and approximately 30 minutes. The annealing may improve strength in the layers of an electrochromic electrode and adhesion of the layers to the first glass substrate 302. Annealing may also reduce charge trapping which improves the faradaic efficiency of the electrochromic electrode.

[0121] Where the first electrochromic layer 308 includes one or more dopants, annealing of the first glass substrate 302 and the layers thereon (including the first electrochromic layer 308) may cause the one or more dopants to migrate toward the broad surfaces of the first electrochromic layer 308 such that one the one or more dopants may effectively sandwich the first electrochromic layer 308. If the first base layer 306 or the first capping layer 310 include one or more dopants, a similar effect may occur for the one or more dopants in these layers.

[0122] Step 202-2, step 204-2, step 206-2, step 208-2, step 210-2, and step 212-2 may be substantially similar to step 202-1 , step 204-1 , step 206-1 , step 208-1 , step 210-1 , and step 212-1 , respectively. In some embodiments, the conversion of the one or more metal-containing precursors into the one or more metal oxides at step 210-2 may utilize one or more different processes than the one or more processes utilized at step 210-1. For example, step 210-2 may include exposing the one or more metal-containing precursors to ultraviolet radiation for between approximately 5minutes and approximately 60 minutes, such as between approximately 10 minutes and approximately 20 minutes. In some embodiments, the relative humidity during step 212-2 is between approximately 30% and approximately 60%.

[0123] As another example, step 212-2 may include annealing at least the second electrochromic layer at one or more temperatures between approximately 100 °C and approximately 400 °C. In some embodiments, step 212-2 may include annealing at least the second electrochromic layer at a temperature of approximately 300 °C. The annealing at step 212-2 may take between approximately 5 minutes and approximately 60 minutes, such as between approximately 10 minutes and approximately 30 minutes. The annealing may improve strength in the layers of an electrochromic electrode and adhesion of the layers to the second glass substrate. Annealing may also reduce charge trapping which improves the faradaic efficiency of the electrochromic electrode.

[0124] The output of step 212-1 is an anodic electrochromic electrode 100. The anodic electrochromic electrode 100 may be heat-strengthened or tempered despite the presence of the first electrically conductive layer 304, the (optional) first base layer 306, the first electrochromic layer 308, and the (optional) first capping layer 310. Similarly, the output of step 212-2 is a cathodic electrochromic electrode 120 that may be heat-strengthened or tempered despite the presence of a second electrically conductive layer, an (optional) second base layer, a second electrochromic layer, and an (optional) second capping layer. In some embodiments, non-heat-strengthened and non-tempered electrochromic electrodes may be manufactured by a glass manufacturer in a small number of relatively large sizes to be cut down and heat-strengthened or tempered as needed for end-customers. In this way, the glass manufacturer may focus on manufacturing a small number of sizes of non-heat-strengthened and non-tempered electrochromic electrodes rather than needing to make heat-strengthened or tempered electrochromic electrodes in individual sizes to order. Accordingly, manufacturing processes may be improved and throughput increased.

[0125] In some embodiments, after step 212-1 and step 212-2, the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 are transported to another entity (for example, a glass fabricator) for subsequentprocessing, described in step 214-1 through step 218-1 and in step 214-2 through step 218-2. However, in various embodiments, the same entity that performed step 202-1 through step 212-1 and step 202-2 through step 212-2 (for example, the glass manufacturer) performs step 214-1 through step 218-1 and step 214-2 through step 218-2.

[0126] At step 214-1 and 214-2, the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 are cut to specified dimensions (for example, according to the needs of a particular consumer). The anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 may be cut using conventional techniques such as, for example, manual scoring and breaking, water jet cutting, laser cutting, CNC (Computer Numerical Control) cutting, diamond saw cutting, ultrasonic cutting, and hot wire cutting.

[0127] In some embodiments, at step 216-1 , portions of one or more layers of the anodic electrochromic electrode 100 (for example, the anodic electrochromic layer 108 and at least one of the base layer 106 and the capping layer 110) are removed around a perimeter of the glass substrate 102 to expose the electrically conductive layer 104. Doing so may enable the coupling of first electrical connectors such as busbars to the electrically conductive layer 104 (for example, at step 220-1 , discussed further herein). Similarly, at step 216-2, portions of one or more layers of the cathodic electrochromic electrode 120 (for example, the cathodic electrochromic layer 128 and at least one of the base layer 126 and the capping layer 130) are removed around a perimeter of the glass substrate 122 to expose the electrically conductive layer 124. Doing so may enable the coupling of second electrical connectors such as busbars to the electrically conductive layer 124 (for example, at step 220-2, discussed further herein).

[0128] The anodic electrochromic electrode 100 may be heat-strengthened or tempered at step 218-1 . Similarly, the cathodic electrochromic electrode 120 may be heat-strengthened or tempered at step 218-2. Heat-strengthening or tempering of the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 may include, for example, heating the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 to one or more temperatures between approximately 600 °C and approximately 700 °C, such as approximately 640° C.After heating the anodic electrochromic electrode 100, the anodic electrochromic electrode 100 may be rapidly cooled in order to heat-strengthen or temper the anodic electrochromic electrode 100. Similarly, after heating the cathodic electrochromic electrode 120, the cathodic electrochromic electrode 120 may be rapidly cooled in order to heat-strengthen or temper the cathodic electrochromic electrode 120. The rate of cooling of the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 may be dependent on, for example, the thickness of the glass substrate 102 and the glass substrate 122, respectively, target surface compressions, target edge compressions, whether the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 are to be heat- strengthened or tempered, or other factors. The output of step 218-1 and step 218-2 are the anodic electrochromic electrode 100 that has been heat-strengthened or tempered and the cathodic electrochromic electrode 120 that has been heat- strengthened or tempered, respectively. The anodic electrochromic electrode 100 or the cathodic electrochromic electrode 120 may also be bent, curved, or otherwise manipulated into a specified shape at step 218-1 or at step 218-2, respectively.

[0129] At step 220-1 and step 220-2, one or more first electrical connectors and one or more second electrical connectors are coupled to the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120, respectively. The electrical connectors may each comprise, for example, a bus (for example, a copper busbar, an ultrasonic soldering busbar, or a plasma sprayed conductive frit / busbar) for connecting to a power source, control hardware, or software. Such busbars may be applied to each of the heat-strengthened or tempered electrochromic electrodes to facilitate electrical charge transfer to the electrically conductive substrate. A pigtail may be provided to allow connection of an electrical supply to the conductive glass substrates. Busbars may be applied prior to a sealant, and can be encapsulated by the sealant.

[0130] After step 220-1 and step 220-2, the method 200 may continue to step 222 where the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120 are assembled together with an electrolyte positioned between the anodic electrochromic electrode 100 and the cathodic electrochromic electrode 120, thereby forming an assembly. The electrolyte, which may also be referred to as anelectrolyte layer, an ion-conducting or ion-conductive layer, or an ion-conducting or ion-conductive electrolyte layer, may include any suitable electrolyte capable of conducting ions. The electrolyte may include one or more ion-conducting salts such as lithium salt or sodium salt. Such salts may be incorporated into various polymer matrices. Such polymer matrices may comprise, for example, polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), acrylic, ionomer, and ethylene-vinyl acetate (EVA). Such a polymer matrix may provide added benefits such as flexibility, transparency, and chemical resistance, contributing to the efficient operation and durability of an electrochromic device. The electrolyte may be in the form of a film. In some embodiments, the electrolyte is a polyvinyl butyral (PVB) interlayer, such as those described in PCT Application No. PCT / CA2024 / 051627, filed December s, 2024 and titled “PROCESSES FOR PREPARING ION-CONDUCTING PVB MATERIALS AND FILMS AND ASSOCIATED MATERIALS, FILMS, AND DEVICES,” the entirety of which is incorporated herein by reference in jurisdictions allowing such incorporation. Positioning the electrolyte may utilize any suitable techniques such as, for example, one drop filing, multi-drop filling, injection filling, and sheet lamination. The electrolyte may be sealed between the first heat- strengthened or tempered electrochromic electrode and the second heat- strengthened or tempered electrochromic electrode. The assembly may be laminated.

[0131] In some embodiments, the entirety of the method 200 is performed by a single entity. In various embodiments, a first entity (for example, a glass manufacturer) performs step 202-1 through step 212-1 and step 202-2 through step 212-2. The first entity then provides the electrochromic electrodes to a second entity (for example, a glass fabricator) that performs step 214-1 through step 220-1 and step 214-2 through step 220-2. The second entity may perform step 222, or the second entity may provide the heat-strengthened or tempered electrochromic electrodes to a third entity (for example, a window installation company) that performs step 222. Other variations of the method 200 will be apparent.

[0132] Fig. 4A is a schematic representation of a curved electrochromic device 401 according to various embodiments. The curved electrochromic device 401 may be a curved electrochromic window such as a sunroof, a windshield, or a window for anautomobile. The curved electrochromic device 401 includes an anodic electrochromic electrode 400T that has been heat-strengthened or tempered, a cathodic electrochromic electrode 420T that has been heat-strengthened or tempered, and an electrolyte 416.

[0133] The anodic electrochromic electrode 400T includes a first glass substrate 402, a first electrically conductive layer 404, and an anodic electrochromic layer 408. The anodic electrochromic electrode 400T also includes a first base layer 406 between the first electrically conductive layer 404 and the anodic electrochromic layer 408 and a first capping layer 410 on the anodic electrochromic layer 408. The anodic electrochromic electrode 400T may also include one or more dopants (not illustrated in Fig. 4A) in the anodic electrochromic layer 408. In some embodiments, the anodic electrochromic electrode 400T does not include one or both of the first base layer 406 and the first capping layer 410. In embodiments where the anodic electrochromic electrode 400T includes neither the first base layer 406 nor the first capping layer 410, the anodic electrochromic electrode 400T may include one or more dopants in the anodic electrochromic layer 408.

[0134] The cathodic electrochromic electrode 420T includes a second glass substrate 422, a second electrically conductive layer 424, and a cathodic electrochromic layer 428. The cathodic electrochromic electrode 420T also includes a second base layer 426 between the second electrically conductive layer 424 and the cathodic electrochromic layer 428 and a second capping layer 430 on the cathodic electrochromic layer 428. The cathodic electrochromic electrode 420T may also include one or more dopants (not illustrated in Fig. 4B) in the cathodic electrochromic layer 428. In some embodiments, the cathodic electrochromic electrode 420T does not include one or both of the second base layer 426 and the second capping layer 430. In embodiments where the cathodic electrochromic electrode 420T includes neither the second base layer 426 nor the second capping layer 430, the cathodic electrochromic electrode 420T may include one or more dopants in the cathodic electrochromic layer 428.

[0135] The curved electrochromic device 401 also includes a first seal 440a and a second seal 440b positioned around certain layers of the anodic electrochromic electrode 400T, certain layers of the cathodic electrochromic electrode 420T, and theelectrolyte 416. The curved electrochromic device 401 also includes a first bus bar 438a positioned proximate to the first electrically conductive layer 404 and a second bus bar 438b positioned proximate to the second electrically conductive layer 424. The first seal 440a and the second seal 440b may function to prevent or reduce ingress of water or other contaminants. In certain embodiments of the curved electrochromic device 401 , if no electrical bias is applied, ions (for example, lithium ions) are stored in the anodic electrochromic layer 408 and the curved electrochromic device 401 is in a transparent state. If an electrical bias is applied to the first bus bar 438a and the second bus bar 438b, ions (for example, lithium ions) migrate from the anodic electrochromic layer 408 across the electrolyte 416 to be stored in the cathodic electrochromic layer 428, and the curved electrochromic device 401 transitions to a coloured state. The curved electrochromic device 401 may include other components not illustrated in Fig. 4A.

[0136] Fig. 4B is a schematic representation of a flat electrochromic device 451 according to various embodiments. The flat electrochromic device 451 may be an electrochromic insulated glass unit to be assembled in a window frame and installed in a building such as a home or an office building. The flat electrochromic device 451 includes an anodic electrochromic electrode 450T that has been heat-strengthened or tempered, a cathodic electrochromic electrode 470T that has been heat- strengthened or tempered, and an electrolyte 466.

[0137] The anodic electrochromic electrode 450T includes a first glass substrate 452, a first electrically conductive layer 454, and an anodic electrochromic layer 458. The anodic electrochromic electrode 450T also includes a first base layer 456 between the first electrically conductive layer 454 and the anodic electrochromic layer 458 and a first capping layer 460 on the anodic electrochromic layer 458. The anodic electrochromic electrode 450T may also include one or more dopants (not illustrated in Fig. 4A) in the anodic electrochromic layer 458. In some embodiments, the anodic electrochromic electrode 450T does not include one or both of the first base layer 456 and the first capping layer 460. In embodiments where the anodic electrochromic electrode 450T includes neither the first base layer 456 nor the first capping layer 460, the anodic electrochromic electrode 450T may include one or more dopants in the anodic electrochromic layer 458.

[0138] The cathodic electrochromic electrode 470T includes a second glass substrate 472, a second electrically conductive layer 474, and a cathodic electrochromic layer 478. The cathodic electrochromic electrode 470T also includes a second base layer 476 between the second electrically conductive layer 474 and the cathodic electrochromic layer 478 and a second capping layer 480 on the cathodic electrochromic layer 478. The cathodic electrochromic electrode 470T may also include one or more dopants (not illustrated in Fig. 4B) in the cathodic electrochromic layer 478. In some embodiments, the cathodic electrochromic electrode 470T does not include one or both of the second base layer 476 and the second capping layer 480. In embodiments where the cathodic electrochromic electrode 470T includes neither the second base layer 476 nor the second capping layer 480, the cathodic electrochromic electrode 470T may include one or more dopants in the cathodic electrochromic layer 478.

[0139] The flat electrochromic device 451 also includes a first seal 490 and a second seal 492. The first seal 490 and the second seal 492 may function to prevent or reduce ingress of water or other contaminants into the flat electrochromic device 451 . The flat electrochromic device 451 also includes a third pane of glass 496 and a spacer 494 positioned between the second glass substrate 472 and the third pane of glass 496. The spacer 494 may be aluminum or another suitable material. The flat electrochromic device 451 may include other components not illustrated in Fig. 4B, such as bus bars or other electrical connectors or coatings.

[0140] In certain embodiments of the flat electrochromic device 451 , if no electrical bias is applied, ions (for example, lithium ions) are stored in the anodic electrochromic layer 458 and the flat electrochromic device 451 is in a transparent state. If an electrical bias is applied to the flat electrochromic device 451 , ions (for example, lithium ions) migrate from the anodic electrochromic layer 458 across the electrolyte 466 to be stored in the cathodic electrochromic layer 478, and the flat electrochromic device 451 transitions to a coloured state.

[0141] The processes described herein may be utilized in the manufacture of various electrochemical devices, such as electrochromic devices, fuel cells, batteries, electrolyzers, supercapacitors, and sensors. Examples of electrochromic devices include, but are not limited to, electrochromic windows (for example,architectural windows, automotive windows, aircraft cabin windows, windows on marine vessels, etc.), electrochromic sunroofs, electrochromic mirrors (for example, rear-view or side-view vehicle mirrors that automatically darken to reduce glare from headlights of behind vehicles), electrochromic displays, electrochromic eyewear (for example, adaptive googles or sunglasses), electrochromic curtains or blinds, electrochromic panels for building facades, electrochromic indicators, wearable electrochromic textiles (for example, clothing with color-changing properties), electrochromic panels or artworks, and electrochromic devices for privacy control (for example, privacy glass in conference rooms).

[0142] Examples of electrochromic devices may also include devices prior to final assembly or operation of the example electrochromic devices in the preceding paragraph. For example, an electrochromic laminated glass unit, which may include an anodic electrochromic electrode, an ion-conductive interlayer, and a cathodic electrochromic electrode that are assembled together in a lamination process, is an electrochromic device. As another example, an electrochromic insulated glass unit includes an electrochromic laminated glass unit assembled with one or more glass panes separated by a gap between the electrochromic laminated glass unit and the one or more glass panes. Other examples of electrochromic devices will be apparent.

[0143] Specific examples are now 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.Example 1

[0144] In a first example, an anode comprising a substrate, a conductive layer, an electrochromic layer and a capping layer was prepared. A solution for forming the electrochromic layer composed of NiSiMgLi (100:10:5:30, by molar ratio) was prepared from nickel 2-ethylhexanoate, partially hydrolyzed tetraethylorthosilicate, magnesium acetate, and lithium methoxide. Precursors were dissolved in ethanol in the appropriate molar ratios referenced to a 0.2M nickel 2-ethylhexanoate solution. Afluorine doped tin oxide (FTO) conductive layer was layered on the substrate and plasma treated to improve wetting of the film. The precursor was then spray coated onto the FTO conductive layer to form the electrochromic layer and the film was decomposed at 300 °C for 30 minutes. Additional layers were added using the same method to reach the desired thickness of the electrochromic layer. A capping layer was then spray coated on top of the electrochromic film using a 0.04M solution of zirconium 2-ethylhexanoate in butanol. The capping layer was decomposed at 300 °C for 30 minutes. The resulting anode was tempered at 640 °C. The anode was then half-cell tested in an argon-filled glovebox. The half-cell setup consisted of a lithium foil reference electrode, lithium foil counter (complementary) electrode, 0.05M LiTFSI in propylene carbonate electrolyte, and a spectrometer to measure the transmittance modulation of the film. The charge capacity of the anode before and after tempering were 10.07mC / cm2and 9.84mC / cm2, respectively, displaying negligible loss in charge capacity. The transmittance modulation of the anode before and after tempering were 45% and 44%, respectively. The anode showed no notable shift in transmittance, color, or haze, in the bleached or colored state after tempering.Example 2

[0145] In a second example, a cathode comprising a substrate, a conductive layer and an electrochromic layer was prepared. A solution for forming an electrochromic layer having a composition of WSiLi (100:10:40, by molar ratio) was prepared from tungsten hexachloride, partially hydrolyzed tetraethylorthosilicate, and lithium methoxide. Precursors were dissolved in ethanol in the appropriate molar ratios referenced to a 0.05M tungsten hexachloride solution. A fluorine doped tin oxide (FTO) conductive layer was layered on the substrate and plasma treated to improve wetting of the film. The precursor was then spray coated onto the FTO conductive layer to form the electrochromic layer and the film was decomposed under UV for 10 minutes. Additional layers were added using the same method to reach the desired thickness of the electrochromic layer. The film was annealed at 300 °C for 30 minutes. The resulting film was tempered at 640 °C. It was then half-cell tested in an argon-filled glovebox. The half-cell setup consisted of a lithium foil reference electrode, lithium foil counter (complementary) electrode, 0.05M LiTFSI in propylene carbonate electrolyte, and a spectrometer to measure the transmittance modulationof the film. The charge capacity of the electrode before and after tempering were 24.15mC / cm2and 9.89mC / cm2, respectively. The transmittance modulation of the electrodes before and after tempering were 73% and 40%, respectively. The dark state transmittance shifted up due to the lower charge capacity after tempering; however, there was no notable shift in transmittance, color, or haze in the bleached state.

[0146] The following are additional examples of devices, processes, or systems according to various embodiments.

[0147] In some aspects, the techniques described herein relate to an electrochromic electrode including: a substrate; a conductive layer; an electrochromic layer including a bulk electrochromic material; and at least one of: a base layer interposed between the conductive layer and the electrochromic layer; a capping layer layered on top of the electrochromic layer; and a metal oxide dopant mixed with the bulk electrochromic material of the electrochromic layer. In some aspects, the techniques described herein relate to an electrochromic electrode or any other claim herein wherein the substrate includes glass, such as float glass.

[0148] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the substrate includes indium tin oxide (ITO), fluorine doped tin oxide (FTO), or aluminum zinc oxide (AZO).

[0149] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx and CeTiOx, such as one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx NiSiMgLiOx, and NiNbLiOx, one or more of NiSiLiOx NiSiMgLiOx, and NiNbLiOx, or one or more of LiNiOx, NiSiLiOx, NiNbLiOx NiSiMgLiOx, and NiAILiOx.

[0150] In some aspects, the techniques described herein relate to an electrochromic electrode wherein a ratio of Li relative to Ni in the bulk electrochromic material is between approximately 0.01-3.0 mol. Li per mol. of Ni, betweenapproximately 0.1 -2.0 mol. Li per mol. of Ni, between approximately 0.05-1.0 mol. Li per mol. of Ni, or between approximately 0.05-0.5 mol. Li per mol. of Ni.

[0151] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer comprises NiSiLiOx, and a ratio of Li relative to Ni in the bulk electrochromic material is between approximately 0.01-1.0 mol. Li per mol. of Ni, between approximately 0.01-0.6 mol. Li per mol. of Ni, between approximately 0.01- 0.4 mol. Li per mol. of Ni, or between approximately 0.05-0.4 mol. Li per mol. of Ni.

[0152] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer comprises NiSiLiOx, and a ratio of Si relative to Ni in the bulk electrochromic material is between approximately 0.01-3.0 mol. Si per mol. of Ni, between approximately 0.05-0.5 mol. Si per mol. of Ni, between approximately 0.05- 0.4 mol. Si per mol. of Ni, or between approximately 0.05-0.2 mol. Si per mol. of Ni.

[0153] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes NiNbLiOx, and a ratio of Li relative to Ni in the bulk electrochromic material is between approximately 0.5-2.0 mol. Li per mol. of Ni, between approximately 1.0-2.0 mol. Li per mol. of Ni. In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes NiNbLiOx, and a ratio of Nb relative to Ni in the bulk electrochromic material is between approximately 0.01- 1 .0 mol. Nb per mol. of Ni, between approximately 0.05-0.8 mol. Nb per mol. of Ni, or between approximately 0.1 -0.6 mol. Nb per mol. of Ni.

[0154] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer is NiSiMgLiOx, and a ratio of Si, Mg and Li relative to Ni in the bulk electrochromic material is between approximately 1.5-2.0 mol. Si, Mg and Li per mol. Ni, between approximately 0.75-2.0 mol. Si, Mg and Li per mol. Ni, or is approximately 0.45 mol. Si, Mg and Li per mol. Ni.

[0155] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer is NiSiMgLiOx, and a ratio of Si relative to Mg in the bulk electrochromic material is between approximately 0.5-4.0 mol. Si per mol. Mg, between approximately 1.0-3.0 mol. Si per mol. Mg, or is approximately 2.0 mol. Si per mol. Mg.

[0156] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes Ni oSiioMgsLisoOx.

[0157] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes NiSiMgLiOx, with a molar ratio of Ni:Si:Mg: Li of 100:10:5:30.

[0158] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes NiSiMgLiOx, with a molar ratio of Ni: Si: Mg: Li of a:b:c:d, where a is between approximately 80 and 120, b is between approximately 8 and 12, c is between approximately 4 and 6 and d is between approximately 24 and 36.

[0159] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx and NbOx.

[0160] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes one or more of WLiAIOx, WSiLiOx, WNbLiOx and WNbLiSiOx.

[0161] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes one or more of WLiAIOx, WSiLiOx and WNbLiOx.

[0162] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes one or more of LiWOx, WLiAIOx, WSiLiOx, WNbLiOx and WNbLiSiOx.

[0163] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes WLiAIOx and a ratio of Al relative to W in the bulk electrochromic material is between approximately 0.01-1.0 mol. Al per mol. of W, between approximately 0.05-0.7 mol. Al per mol. of W, between approximately 0.05- 0.5 mol. Al per mol. of W, or between approximately 0.1 -0.5 mol. Al per mol. of W.

[0164] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes WSiLiOx and a ratio of Si relative to W in the bulk electrochromic material is between approximately 0.01-1.0 mol. Si per mol. of W, between approximately 0.05-0.7 mol. Si per mol. of W, between approximately 0.05- 0.5 mol. Si per mol. of W, or between approximately 0.1 -0.5 mol. Si per mol. of W.

[0165] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the bulk electrochromic material of the electrochromic layer includes WNbLiOx and a ratio of Nb relative to W in the bulk electrochromic material is between approximately 0.01-1.0 mol. Nb per mol. of W, between approximately 0.05-0.7 mol. Nb per mol. of W, between approximately 0.05- 0.5 mol. Nb per mol. of W, between approximately 0.1 -0.5 mol. Nb per mol. of W.

[0166] In some aspects, the techniques described herein relate to an electrochromic electrode a ratio of Li relative to W in the bulk electrochromic material is between approximately 0.05-1.0 mol. Li per mol. of W, between approximately 0.1- 0.7 mol. Li per mol. of W, or between approximately 0.1 -0.5 mol. Li per mol. of W.

[0167] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrochromic layer includes one or more templating agents, such as one or more of PLURONIC™ P123, TRITON™ X-100surfactant, PLURONIC™ F127, Polyethylene glycol) (PEG) and Polyvinylpyrrolidone (PVP).

[0168] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrochromic layer includes one or more lithium salts.

[0169] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the base layer includes one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, ITO, SiOx, WOx, CuOx and SnOx, one or more of TiOx, CeOx, ZrOx, CeTiOx and InOx, or one or more of TiOx, CeOx, CeTiOx and InOx.

[0170] In some aspects, the techniques described herein relate to an electrochromic electrode wherein a coefficient of thermal expansion of the base layer is between a coefficient of thermal expansion of the conductive layer and a coefficient of thermal expansion of the electrochromic layer.

[0171] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the metal oxide dopant includes one or more metal oxides.

[0172] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the metal oxide dopant includes one or more metal oxides wherein the metals of the one or more metal oxides are selected from the group consisting of: niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium.

[0173] In some aspects, the techniques described herein relate to an electrochromic electrode wherein bulk electrochromic material includes one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, and NiNbLiOx and the metal oxide dopant includes one or more metal oxides wherein the metals of the one or more metal oxides are selected from the group consisting of: cerium, aluminum, tantalum, molybdenum, titanium, indium, magnesium, yttrium, boron, fluorine, gallium,germanium, hafnium, lanthanum, sodium, phosphorus, antimony, selenium, vanadium, tungsten, zinc, and zirconium.

[0174] In some aspects, the techniques described herein relate to an electrochromic electrode wherein bulk electrochromic material includes one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, and NiNbLiOx and the metal oxide dopant includes one or more metal oxides wherein the metals of the one or more metal oxides are selected from the group consisting of: cerium, aluminum, tantalum, molybdenum, titanium, indium, magnesium, yttrium, boron, fluorine, gallium, germanium, lanthanum, sodium, phosphorus, vanadium, tungsten, zinc, and zirconium.

[0175] In some aspects, the techniques described herein relate to an electrochromic electrode wherein a ratio of the metal oxide dopant to the bulk electrochromic material in the electrochromic layer is between approximately 0.005 to approximately 1 .0 mol. dopant per mol. of bulk electrochromic material, between approximately 0.005 to approximately 0.5 mol. dopant per mol. of bulk electrochromic material, between approximately 0.005 to approximately 0.4 mol. dopant per mol. of bulk electrochromic material, or between approximately 0.005 to approximately 0.2 mol. dopant per mol. of bulk electrochromic material.

[0176] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the capping layer includes one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx or one or more of ZrOx, ZnOx, MgOx, NbOx, CeOx and CeTiOx.

[0177] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the base layer has a thickness of between approximately 5nm and 500nm, between approximately 5nm and 300nm, or between approximately 5nm and 200nm.

[0178] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the electrochromic layer has a thickness of between approximately 100nm and 2000nm, between approximately 300nm and 1500nm, between approximately 400nm and 1300nm, between approximately100nm and 1500nm, between approximately 200nm and 1000nm, or between approximately 200nm and 600nm.

[0179] In some aspects, the techniques described herein relate to an electrochromic electrode wherein the capping layer has a thickness of between approximately 50nm and 500nm, between approximately 50nm and 400nm, or between approximately 50nm and 300nm.

[0180] In some aspects, the techniques described herein relate to an electrochromic electrode including the base layer interposed between the conductive layer and the electrochromic layer.

[0181] In some aspects, the techniques described herein relate to an electrochromic electrode including the capping layer layered on top of the electrochromic layer.

[0182] In some aspects, the techniques described herein relate to an electrochromic electrode including the metal oxide dopant mixed with the bulk electrochromic material of the electrochromic layer.

[0183] In some aspects, the techniques described herein relate to an electrochromic device including: an electrolyte between a first electrochromic electrode and a second electrochromic electrode wherein the first electrochromic electrode includes the electrochromic electrode herein.

[0184] In some aspects, the techniques described herein relate to an electrochromic device or any other claim herein wherein the electrolyte includes a lithium salt, or a sodium salt optionally incorporated into a polymer matrix including one or more of polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), acrylic, ionomer, and ethylene-vinyl acetate (EVA).

[0185] In some aspects, the techniques described herein relate to an electrochromic device including: an electrolyte between an electrochromic anode and an electrochromic cathode wherein: the electrochromic anode includes: a first substrate; a first conductive layer; a first electrochromic layer including a first bulk electrochromic material; and at least one of: a first base layer interposed betweenthe first conductive layer and the first electrochromic layer; a first capping layer layered on top of the first electrochromic layer; and a first dopant mixed with the first bulk electrochromic material of the first electrochromic layer; and the electrochromic cathode includes:, a second substrate; a second conductive layer; a second electrochromic layer including a second bulk electrochromic material; and at least one of: a second base layer interposed between the second conductive layer and the second electrochromic layer; a second capping layer layered on top of the second electrochromic layer; and a second dopant mixed with the second bulk electrochromic material of the second electrochromic layer.

[0186] In some aspects, the techniques described herein relate to an electrochromic electrode including: a substrate; a conductive layer; an electrochromic layer including a bulk electrochromic material; and a base layer between the conductive layer and the electrochromic layer.

[0187] In some aspects, the techniques described herein relate to an electrochromic electrode including: a substrate; a conductive layer; an electrochromic layer including a bulk electrochromic material; and a capping layer layered on top of the electrochromic layer.

[0188] In some aspects, the techniques described herein relate to an electrochromic electrode including: a substrate; a conductive layer; an electrochromic layer including a bulk electrochromic material; and a dopant mixed with the bulk electrochromic material.

[0189] In some aspects, the techniques described herein relate to a method of fabricating an electrochromic electrode, the method including: layering a film on a substrate; and curing the film on the substrate; wherein layering the film on the substrate includes layering a conductive layer on the substrate; layering an electrochromic layer on the conductive layer, the electrochromic layer including a bulk electrochromic material; and at least one of: interposing a base layer between the conductive layer and the electrochromic layer; layering a capping layer on top of the electrochromic layer; and mixing a dopant with the bulk electrochromic material of the electrochromic layer.

[0190] In some aspects, the techniques described herein relate to a method of fabricating an electrochromic electrode, the method including: layering a film on a substrate; and curing the film on the substrate; wherein layering the film on the substrate includes layering a conductive layer on the substrate; layering an electrochromic layer on the conductive layer, the electrochromic layer including a bulk electrochromic material; and interposing a base layer between the conductive layer and the electrochromic layer.

[0191] In some aspects, the techniques described herein relate to a method of fabricating an electrochromic electrode, the method including: layering a film on a substrate; and curing the film on the substrate; wherein layering the film on the substrate includes layering a conductive layer on the substrate; layering an electrochromic layer on the conductive layer, the electrochromic layer including a bulk electrochromic material; and layering a capping layer on top of the electrochromic layer.

[0192] In some aspects, the techniques described herein relate to a method of fabricating an electrochromic electrode, the method including: layering a film on a substrate; and curing the film on the substrate; wherein layering the film on the substrate includes layering a conductive layer on the substrate; layering an electrochromic layer on the conductive layer, the electrochromic layer including a bulk electrochromic material; and mixing a dopant with the bulk electrochromic material of the electrochromic layer. In some aspects, the method further includes annealing the film on the substrate after curing the film on the substrate. In some aspects, the method further includes cutting the substrate and the film to a desired size. In some aspects, the method further includes tempering the film and the substrate after layering the film on the substrate.

[0193] In some aspects, the techniques described herein relate to an electrochromic electrode or electrochromic device wherein the bulk electrochromic material is capable of withstanding tempering or heating treating. In some aspects, the bulk electrochromic material is capable of withstanding tempering or heatstrengthening at a temperature of between approximately 600 °C and 700 °C. In some aspects, the bulk electrochromic material is capable of withstanding tempering or heat-strengthening at a temperature of approximately 640 °C.

[0194] 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, 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.

[0195] 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.

[0196] Where a component is referred to herein, unless otherwise indicated, reference to that component (including a reference to a “means”) should be interpreted as including as equivalents of that component any component which performs the function of the described component (functionally equivalent), including components which are not structurally equivalent to the disclosed structure, but which performs the function in the illustrated exemplary embodiments.

[0197] 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 componentsmay cooperate or interact with each other, and may be in direct or indirect physical, electrical, or communicative contact with each other.

[0198] 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.

[0199] 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.”

[0200] 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. As another example, individual coatings may be applied to the substrate and then processed (individually or collectively) to form layers. Collectively, the processed layers may be referred to as a single layer. As another example, one or more films may be prepared for one or more of the layers using various techniques (for example, extrusion) and then applied to a glass substrate. The films and the glass substrate may be processed to form an electrochromic electrode. The electrochromic electrode may then be heat- strengthened or tempered.

Claims

CLAIMS l / We claim:1 . A process for manufacturing an electrochromic electrode, the process comprising: forming an electrically conductive layer on a glass substrate, wherein the glass substrate is not heat-strengthened or tempered; applying a solution on a layer on the glass substrate, wherein the solution includes one or more metal-containing precursors to be converted into one or more metal oxides; converting the one or more metal-containing precursors into the one or more metal oxides to form an electrochromic layer on the layer, wherein the electrochromic layer includes the one or more metal oxides; and performing one or more of: prior to applying the solution on the layer, forming a base layer on the electrically conductive layer, wherein the base layer includes first material, and applying the solution on the layer includes applying the solution on the base layer; forming a capping layer on the electrochromic layer, wherein the capping layer includes second material; and applying one or more dopants on the layer with the one or more metalcontaining precursors.

2. The process of claim 1 wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes exposing the one or more metal-containing precursors to one or more of ultraviolet radiation, infrared radiation, and ozone to form the electrochromic layer on the layer.

3. The process of claim 1 wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes exposing the one or more metal-containing precursors to one or more temperatures of approximately 150 °C to approximately 650 °C to form the electrochromic layer on the layer.

4. The process of claim 3 wherein exposing the one or more metal-containing precursors to the one or more temperatures of approximately 150 °C to approximately 650 °C to form the electrochromic layer on the layer is a first exposure that is performed prior to forming the capping layer on the electrochromic layer, the one or more temperatures are one or more first temperatures, and the capping layer on the electrochromic layer is formed by a second exposure to one or more second temperatures of approximately 150 °C to approximately 650 °C.

5. The process of any of claims 2 to 4, further comprising annealing at least the electrochromic layer.

6. The process of claim 1 wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes converting the one or more metal-containing precursors into one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx to form an anodic electrochromic layer on the layer.

7. The process of claim 1 wherein converting the one or more metal-containing precursors into the one or more metal oxides to form the electrochromic layer on the layer includes converting the one or more metal-containing precursors into one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx to form a cathodic electrochromic layer on the layer.

8. The process of claim 1 wherein the solution further includes one or more templating agents or one or more lithium salts.

9. The process of claim 1 wherein the first material includes one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.

10. The process of claim 1 wherein the second material includes one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.11 .The process of claim 1 wherein the one or more metal oxides are different from both the first material and the second material.

12. The process of claim 1 wherein the one or more dopants include one or more metal or metalloid oxide dopants, and one or more metals or metalloids of the one or more metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium or one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

13. The process of claim 12 wherein a ratio of the one or more metal or metalloid oxide dopants to the one or more metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more metal or metalloid oxide dopants per mol. of the one or more metal oxides.

14. The process of claim 12 wherein the one or more dopants are one or more first dopants, and the process further comprises including one or more second dopants in one or more of the base layer and the capping layer.

15. The process of claim 1 wherein the electrically conductive layer has a first coefficient of thermal expansion, the electrochromic layer has a second coefficient of thermal expansion, and the base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

16. An electrochromic electrode manufactured according to the process of any of claims 1 to 15.

17. An electrochromic electrode comprising: a glass substrate, the glass substrate not heat-strengthened or tempered; an electrically conductive layer;an electrochromic layer including one or more metal oxides; and one or more of: a base layer between the electrically conductive layer and the electrochromic layer, the base layer including first material; a capping layer on the electrochromic layer, the capping layer including second material; and one or more dopants included in the electrochromic layer.

18. The electrochromic electrode of claim 17 wherein the electrochromic layer is an anodic electrochromic layer and the one or more metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx.

19. The electrochromic electrode of claim 17 wherein the electrochromic layer is a cathodic electrochromic layer and the one or more metal oxides include one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx.

20. The electrochromic electrode of claim 17 wherein the first material includes one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.21 . The electrochromic electrode of claim 17 wherein the second material includes one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

22. The electrochromic electrode of claim 17 wherein the one or more metal oxides are different from both the first material and the second material.

23. The electrochromic electrode of claim 17 wherein the one or more dopants include one or more metal or metalloid oxide dopants, and one or more metals or metalloids of the one or more metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium,phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium or one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

24. The electrochromic electrode of claim 23 wherein a ratio of the one or more metal or metalloid oxide dopants to the one or more metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more metal or metalloid oxide dopants per mol. of the one or more metal oxides.

25. The electrochromic electrode of claim 17 wherein the electrically conductive layer has a first coefficient of thermal expansion, the electrochromic layer has a second coefficient of thermal expansion, and the base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

26. The electrochromic electrode of claim 17 wherein the electrochromic electrode is capable of withstanding heat-strengthening or tempering at one or more temperatures between approximately 600 °C and approximately 700 °C while maintaining a specified charge capacity.

27. A process comprising: cutting a first electrochromic electrode to first dimensions, the first electrochromic electrode including: a first glass substrate; a first electrically conductive layer; a first electrochromic layer including one or more first metal oxides; and one or more of: a first base layer between the first electrically conductive layer and the first electrochromic layer, the first base layer including first material; a first capping layer on the first electrochromic layer, the first capping layer including second material; and one or more first dopants included in the first electrochromicheat-strengthening or tempering the first electrochromic electrode to form a first heat-strengthened or tempered electrochromic electrode; cutting a second electrochromic electrode to second dimensions, the second electrochromic electrode complementary to the first electrochromic electrode, the second electrochromic electrode including: a second glass substrate; a second electrically conductive layer; a second electrochromic layer including one or more second metal oxides; and one or more of: a second base layer between the second electrically conductive layer and the second electrochromic layer, the second base layer including third material; a second capping layer on the second electrochromic layer, the second capping layer including fourth material; and one or more second dopants included in the second electrochromic layer; and heat-strengthening or tempering the second electrochromic electrode to form a second heat-strengthened or tempered electrochromic electrode.

28. The process of claim 27 wherein the one or more first metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx, and the first electrochromic layer is an anodic electrochromic layer.

29. The process of claim 27 wherein the one or more second metal oxides include or one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx, and the second electrochromic layer is a cathodic electrochromic layer.

30. The process of claim 27 wherein both the first material and the third material include one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.31 . The process of claim 27 wherein both the second material and the fourth material include one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

32. The process of claim 27 wherein the one or more first metal oxides are different from both the first material and the second material, and the one or more second metal oxides are different from both the third material and the fourth material.

33. The process of claim 27 wherein the one or more first dopants include one or more first metal or metalloid oxide dopants, and one or more first metals or metalloids of the one or more first metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium, and the one or more second dopants include one or more second metal or metalloid oxide dopants, and one or more second metals or metalloids of the one or more second metal or metalloid oxide dopants are one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

34. The process of claim 27 wherein a first ratio of the one or more first dopants to the one or more first metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more first dopants per mol. of the one or more first metal oxides, and a second ratio of the one or more second dopants to the one or more second metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more second dopants per mol. of the one or more second metal oxides.

35. The process of claim 27 wherein the first electrically conductive layer has a first coefficient of thermal expansion, the first electrochromic layer has a second coefficient of thermal expansion, and the first base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

36. The process of claim 27, further comprising: positioning an electrolyte between the first heat-strengthened or tempered electrochromic electrode and the second heat-strengthened or tempered electrochromic electrode; coupling one or more first electrical connectors to the first heat-strengthened or tempered electrochromic electrode; coupling one or more second electrical connectors to the second heat- strengthened or tempered electrochromic electrode; and sealing the electrolyte between the first heat-strengthened or tempered electrochromic electrode and the second heat-strengthened or tempered electrochromic electrode.

37. An electrochromic device manufactured according to the process of claim 36.

38. An electrochromic device comprising: a first heat-strengthened or tempered electrochromic electrode including: a first glass substrate; a first electrically conductive layer; a first electrochromic layer including one or more first metal oxides; and at least one of: a first base layer between the first electrically conductive layer and the first electrochromic layer, the first base layer including first material; a first capping layer on the first electrochromic layer, the first capping layer including second material; and one or more first dopants included in the first electrochromic layer; a second heat-strengthened or tempered electrochromic electrode, the second heat-strengthened or tempered electrochromic electrode complementary to the first heat-strengthened or tempered electrochromic electrode, the second heat- strengthened or tempered electrochromic electrode including: a second glass substrate; a second electrically conductive layer; a second electrochromic layer including one or more second metal oxides; andat least one of: a second base layer between the second electrically conductive layer and the second electrochromic layer, the second base layer including third material; a second capping layer on the second electrochromic layer, the second capping layer including fourth material; and one or more second dopants included in the second electrochromic layer; and an electrolyte between the first heat-strengthened or tempered electrochromic electrode and the second heat-strengthened or tempered electrochromic electrode, wherein the first electrically conductive layer, the first electrochromic layer, and at least one of the first base layer and the first capping layer were formed on the first glass substrate prior to heat-strengthening or tempering the first glass substrate to form the first heat-strengthened or tempered electrochromic electrode, and the second electrically conductive layer, the second electrochromic layer, and at least one of the second base layer and the second capping layer were formed on the second glass substrate prior to heat-strengthening or tempering the second glass substrate to form the second heat-strengthened or tempered electrochromic electrode.

39. The electrochromic device of claim 38 wherein the first electrochromic layer is an anodic electrochromic layer and the one or more first metal oxides include one or more of NiOx, LiNiOx, NiNbOx, NiSiLiOx, NiSiMgLiOx, NiNbLiOx, NiAILiOx, CoOx, IrOx, MnOx, FeOx, VOx, CeOx, and CeTiOx.

40. The electrochromic device of claim 38 wherein the second electrochromic layer is a cathodic electrochromic layer and the one or more second metal oxides include or one or more of WOx, WNbOx, TiWOx, LiWOx, WLiAIOx, WSiLiOx, WNbLiOx, WNbLiSiOx, WNbAIOx, MoOx, TiOx, TaOx, and NbOx.41 . The electrochromic device of claim 38 wherein both the first material and the third material include one or more of TiOx, CeOx, ZrOx, CeTiOx, InOx, indium tin oxide (ITO), SiOx, WOx, CuOx and SnOx.

42. The electrochromic device of claim 38 wherein both the second material and the fourth material include one or more of AIOx, ZrOx, ZnOx, SiOx, BOx, MgOx, NbOx, CeOx and CeTiOx.

43. The electrochromic device of claim 38 wherein the one or more first metal oxides are different from both the first material and the second material, and the one or more second metal oxides are different from both the third material and the fourth material.

44. The electrochromic device of claim 38 wherein the one or more first dopants include one or more first metal or metalloid oxide dopants, and one or more first metals or metalloids of the one or more first metal or metalloid oxide dopants are one or more of niobium, cerium, aluminum, lithium, tantalum, molybdenum, cobalt, silicon, titanium, indium, magnesium, yttrium, boron, calcium, cadmium, chlorine, chromium, fluorine, copper, gallium, gadolinium, germanium, hafnium, lanthanum, manganese, sodium, phosphorus, antimony, selenium, tin, strontium, vanadium, tungsten, zinc, and zirconium, and the one or more second dopants include one or more second metal or metalloid oxide dopants, and one or more second metals or metalloids of the one or more second metal or metalloid oxide dopants are one or more of one or more of silicon, aluminum, niobium, lithium, magnesium, manganese, chromium, cerium, nickel, zinc, cobalt, copper, and titanium.

45. The electrochromic device of claim 44 wherein a first ratio of the one or more first dopants to the one or more first metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more first dopants per mol. of the one or more first metal oxides, and a second ratio of the one or more second dopants to the one or more second metal oxides is between approximately 0.005 and approximately 1 .0 mol. of the one or more second dopants per mol. of the one or more second metal oxides.

46. The electrochromic device of claim 38 wherein the first electrically conductive layer has a first coefficient of thermal expansion, the first electrochromic layer has a second coefficient of thermal expansion, and the first base layer has a third coefficient of thermal expansion that is between the first coefficient of thermal expansion and the second coefficient of thermal expansion.

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