# US 7,746,533 B2 · Electrochromic devices utilizing very low band gap conjugated counter electrodes: preparation and use > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,746,533 B2 - Document ID: US7746533B2 - Status: Granted - Kind: B2 - Application number: 11/456,603 - Filed: 2006-07-11 - Published: 2007-01-11 - Granted: 2010-06-29 - Earliest claimed: 2005-07-11 - Assignees: University of Connecticut - Inventors: Gregory A. Sotzing; Venkataramanan Seshadri - Web page: https://patentgrep.com/patent/US7746533B2 ## CPC - C09K 9/02: Organic tenebrescent materials - G02F 1/1503: caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions - C09K 2211/1441: Heterocyclic - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS ## Abstract Disclosed herein are electrochromic devices using a very low band-gap conjugated polymer having a band gap (Eg) of less than or equal to about 1.5 eV, and having little or no electrochromism in the visible region of the electromagnetic spectrum. ## Claims ### Claim 1 An electrochromic device, comprising: a first layer comprising a first conjugated polymer, wherein the first conjugated polymer has a band gap of less than or equal to about 1.5 eV and an Lmax absorption peak of greater than or equal to about 750 nm in the neutral, oxidized, and reduced forms, and wherein the first layer functions as an ion-storage layer; a second layer comprising a second conjugated polymer, wherein the second conjugated polymer has a band gap of less than about 2.5 eV and wherein the second layer functions as an electrochromic in the visible region of the electromagnetic spectrum; an electrolyte layer disposed between and in contact with the first layer and the second layer; a first electrode in electrical communication with the first layer; and a second electrode in electrical communication with the second layer. ### Claim 2 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer is electrochromic in the infrared region, near infrared region, or both infrared and near infrared regions of the electromagnetic spectrum. ### Claim 3 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer, when oxidized, is absorbing in the infrared region, near infrared region, or both infrared and near infrared regions of the electromagnetic spectrum. ### Claim 4 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer exhibits substantially no absorbance in the visible region of the electromagnetic spectrum when in the neutral, oxidized, and reduced states. ### Claim 5 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer, second conjugated polymer, or a combination thereof has a band gap of less than or equal to about 1.3 eV. ### Claim 6 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer, second conjugated polymer, or a combination thereof has a band gap of less than or equal to about 1.1 eV. ### Claim 7 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer, second conjugated polymer, or a combination thereof has a band gap of less than or equal to about 0.9 eV. ### Claim 8 (depends on 1) The electrochromic device of claim 1, wherein the second conjugated polymer has a band gap of about 1.7 to about 2.2 eV. ### Claim 9 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer comprises units derived from monomers according to the structure (I), (II), or (III): wherein A is S or O; and wherein Ra is hydrogen, hydroxyl, C6-C12 aryl, C3-C10 cycloalkyl, C1-C12 alkyl, halogen, C1-C12 alkoxy, C1-C12 alkylthio, C1-C12 haloalkyl, C1-C12 haloalkoxy, C6-C12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C1-C12 alkylamino, C1-C12 minoalkyl, acyl, sulf oxyl, sulfonyl, sulfonate, phosphonate, amido, or carbamoyl. ### Claim 10 (depends on 9) The electrochromic device of claim 9, wherein the first conjugated polymer is a homopolymer. ### Claim 11 (depends on 9) The electrochromic device of claim 9, wherein Ra is hydrogen or alkyl. ### Claim 12 (depends on 9) The electrochromic device of claim 9, wherein the polymer is a copolymer comprising, in addition to the units derived from monomer (I), (II), or (III), units derived from a co-monomer reactive with monomer (I), (II), or (III). ### Claim 13 (depends on 12) The electrochromic device of claim 12, wherein the co-monomer is thiophene, substituted thiophene, dithieno[3,4-b:3′,4-d]thiophene, bithiophene, pyrrole, substituted pyrrole, or a combination comprising at least one of the foregoing co-monomers, wherein the substituents are one or more of hydroxyl, C6-C12 aryl, C3-C10 cycloalkyl, C1-C12 alkyl, halogen, C1-C12 alkoxy, C1-C12 alkylthio, C1-C12 haloalkyl, C6-C12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C1-C12 alkylamino, C1-C12 aminoalkyl, acyl, sulfoxyl, sulfonyl, sulfonate, phosphonate, amido, carbamoyl, or a combination comprising at least one of the foregoing substituents. ### Claim 14 (depends on 12) The electrochromic device of claim 12, wherein the co-monomer is wherein X1 is S, O, or N—R5, wherein R5 is hydrogen or C1-C12 alkyl; X is C1-C4 alkylene or substituted C1-C4 alkylene; wherein X1 is as previously defined, and wherein R3 and R4 are the same or different and are hydrogen, hydroxyl, C6-C12 aryl, C3-C10 cycloalkyl, C1-C12 alkyl, halogen, C1-12 alkoxy, C1-C12 alkylthio, C1-C12 haloalkoxy, C1-C12 haloalkyl, or C6-C12 halo aryl, —C1-C6 alkyl-O—C1-C6 alkyl, or —C1-C6 alkyl-O—C6-C12 aryl; wherein Q′ is S or O; wherein X1, R2, and R4 are as previously defined, and wherein X2 and X3 are the same or different and are CH or N; wherein X1, Q1, R3, and R2 are as previously defined, and wherein each occurrence of Q1, R3, or R4 may be the same or different; wherein X1 is as previously defined; wherein X1, R3, and R4 are as previously defined, and wherein each occurrence of X1 may be the same or different; wherein X1 is as previously defined, and wherein each occurrence of X1 may be the same or different; and X4 is C(R3)2, S, O, or N—R5, wherein R3 and R5 are as previously defined; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different; wherein X1 is as previously defined, and wherein each occurrence of X1 may be the same or different, and E is O or C(R7)2, wherein each occurrence of R7 is an electron withdrawing group; wherein X1, Q1, and R3 are as previously defined, and wherein each occurrence of X1, Q1, or R3 may be the same or different; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different, and each occurrence of R8 is hydrogen, C1-C6 alkyl, or cyano; wherein X1, R3, and R8 are as previously defined, and wherein each occurrence of X1, R3, or may be the same or different, and each occurrence of Q3 is independently CH2, S, or O; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different, and Ar is a furan, pyrrole, N-substituted pyrrole, phenyl, biphenyl, thiophene, fluorene, or 9-alkyl-9H-carbazole; wherein X1, Q1, R3, and Ar are as previously defined, and wherein each occurrence of X1, Q1, or R3 may be the same or different; wherein X1, X4, Q1, and R3 are as previously defined, and wherein each occurrence of X1, Q1, or R3 may be the same or different; wherein X1, X4, and R3 are as previously defined, and wherein each occurrence of X1 or may be the same or different; wherein X1 and X4 are as previously defined, and wherein each occurrence of X1 or X4 may be the same or different; wherein X1 and Q1 are as previously defined, and wherein each occurrence of Q1 may be the same or different; wherein X1 and Q1 are as previously defined, and wherein each occurrence of X1 or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of R3 or may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; wherein X1, R3, Q1, and Ar are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; or a combination comprising at least one of the foregoing co-monomers. ### Claim 15 (depends on 1) The electrochromic device of claim 1, wherein the first conjugated polymer, the second conjugated polymer, or a combination thereof has been doped with a p-dopant or an n-dopant. ### Claim 16 (depends on 1) The electrochromic device of claim 1, wherein the first and second electrodes are glass-indium doped tin oxide (glass-ITO), poly(3,4-ethyl enedioxythiophene)-polystyrene sulfonate (PEDOT-PSS), thin gold layer, platinum, metal alloys, stainless steel alloys, or nickel alloys. ### Claim 17 (depends on 1) The electrochromic device of claim 1, wherein the electrolyte layer is a gel electrolyte comprising lithium trifluomethanesulfonate, lithium trifluoromethanesulfonimide, tetraalkylammonium hexafluorophosphates, tetraalkylammonium tosylates, or N-alkylimmidazoliunium salts dissolved in a polymer matrix, wherein the polymatrix is a poly(meth)acrylic, a polystyrenic, or a homopolymer or copolymer of polyethyleneglycol; and wherein the gel electrolyte is optionally plasticized. ### Claim 18 (depends on 1) The electrochromic device of claim 1, wherein the device is a display, a flexible color display, an attenuator, or a transmission device. ### Claim 19 An electrochromic device, comprising: a first layer comprising a first conjugated polymer, wherein the first conjugated polymer has a band gap of less than or equal to about 1.5 eV and a Lmax absorption peak of greater than or equal to about 750 nm in the neutral, oxidized, and reduced forms, and wherein the first layer functions as an ion-storage layer; a second layer comprising an ion-chelating inorganic structure that reversibly binds to counter-ions; an electrolyte layer in contact with the first layer and the second layer; a first electrode in electrical communication with the first layer; and a second electrode in electrical communication with the second layer. ### Claim 20 (depends on 19) The electrochromic device of claim 19, wherein the ion-chelating inorganic structure is tungsten oxide, nickel oxide or other metal oxide layers. ### Claim 21 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer is electrochromic in the infrared region, near infrared region, or both infrared and near infrared regions of the electromagnetic spectrum. ### Claim 22 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer, when oxidized, is absorbing in the infrared region, near infrared region, or both infrared and near infrared regions of the electromagnetic spectrum. ### Claim 23 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer exhibits substantially no absorbance in the visible region of the electromagnetic spectrum when in the neutral, oxidized, and reduced states. ### Claim 24 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer has a band gap of less than or equal to about 1.3 eV. ### Claim 25 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer has a band gap of less than or equal to about 1.1 eV. ### Claim 26 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer comprises units derived from monomers according to the structure (I), (II), or (III): wherein A is S or O; and wherein Ra is hydrogen, hydroxyl, C6-C12 aryl, C3-C10 cycloalkyl, C1-C12 alkyl, halogen, C1-C12 alkoxy, C1-C12 alkylthio, C1-C12 haloalkyl, C1-C12 haloalkoxy, C6-C12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C1-C12 alkylamino, C1-C12 aminoalkyl, acyl, sulfoxyl, sulfonyl, sulfonate, phosphonate, amido, or carbamoyl. ### Claim 27 (depends on 26) The electrochromic device of claim 26, wherein the first conjugated polymer is a homopolymer. ### Claim 28 (depends on 26) The electrochromic device of claim 26, wherein Ra is hydrogen or C1-C4 alkyl. ### Claim 29 (depends on 26) The electrochromic device of claim 26, wherein the polymer is a copolymer comprising, in addition to the units derived from monomer (I), (II), or (III), units derived hm a co-monomer reactive with monomer (I), (II), or (III). ### Claim 30 (depends on 29) The electrochromic device of claim 29, wherein the co-monomer is thiophene, substituted thiophene, dithieno[3,4-b:3′,4′-dithiophene, bithiophene, pyrrole, substituted pyrrole, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl, substituted biphenyl, terphenyl, substituted terphenyl, phenylene vinylene, substituted phenylene vinylene, or a combination comprising at least one of the foregoing co-monomers, wherein the substituents are one or more of hydroxyl, C6-C12 aryl, C3-C10 cycloalkyl, C1-C12 alkyl, halogen, C1-C12 alkoxy, C1-C12 alkylthio, C1-C12 haloalkyl, C6-C12 haloaryl, pyridyl, cyano, thiocyanato, nitro, amino, C1-C12 alkylamino, C1-C12 aminoalkyl, acyl, sulfoxyl, sulfonyl, sulfonate, phosphonate, amido, carbamoyl, or a combination comprising at least one of the foregoing substituents. ### Claim 31 (depends on 29) The electrochromic device of claim 29, wherein the co-monomer is wherein X1 is S, O, or N—R5, wherein R5 is hydrogen or C1-C12 alkyl; X is C1-C4 alkylene or substituted C1-C4 alkylene; wherein X1 is as previously defined, wherein R3 and R4 are the same or different and are hydrogen, hydroxyl, C6-C12 aryl, C3-C10 cycloalkyl, C1-C12 alkyl, halogen, C1-C12 alkoxy, C1-C12 alkylthio, C1-C12 haloalkoxy, C1-C12 haloalkyl, or C6-C12 haloaryl, —C1-C6 alkyl-0-C1-C6 alkyl, or —C1-C6 alk1-O—C6-C12 aryl; wherein Q1 is S or O; wherein X1, R3, and R4 are as previously defined, and wherein X2 and X3 are the same or different and are CH or N; wherein X1, Q1, R3, and R4 are as previously defined, and wherein each occurrence of Q1, R3, or R4 may be the same or different; wherein X1 is as previously defined; wherein X1, R3, and R4 are as previously defined, and wherein each occurrence of X1 may be the same or different; wherein X1 is as previously defined; and wherein each occurrence of X1 may be the same or different, and X4 is c(R3)2, S, O, or N—R5, wherein R3 and R5 are as previously defined; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different; wherein X1 is as previously defined, and wherein each occurrence of X1 may be the same or different, and E is O or C(R7)2, wherein each occurrence of R7 is an electron withdrawing group; wherein X1, Q1, and R3 are as previously defined, and wherein each occurrence of X1, Q1, or R3 may be the same or different; wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different, and each occurrence of R8 is hydrogen, C1-C6 alkyl, or cyano; wherein X1, R3, and R8 are as previously defined, and wherein each occurrence of X1, R3, or R8 may be the same or different; and each occurrence of Q3 is independently CH, S or O wherein X1 and R3 are as previously defined, and wherein each occurrence of X1 or R3 may be the same or different, and Ar is a furan, pyrrole, N-substituted pyrrole, phenyl, biphenyl, thiophene, fluorene, or 9-alkyl-9H-carbazole; wherein X1, Q1, R3, and Ar are as previously defined, and wherein each occurrence of X1, Q1, or R3 may be the same or different; wherein X1, X4, Q1, and R3 are as previously defined, and wherein each occurrence of X1, Q1, or R3 may be the same or different; wherein X1, X3, and R3 are as previously defined, and wherein each occurrence of X1 or may be the same or different; wherein X1 and X4 are as previously defined, and wherein each occurrence of X1 or X4 may be the same or different; wherein X1 and Q1 are as previously defined, and wherein each occurrence of Q1 may be the same or different; wherein X1 and Q1 are as previously defined, and wherein each occurrence of X1 or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of R3 or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; wherein X1, R3, Q1, and Ar are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; wherein X1, R3, and Q1 are as previously defined, and wherein each occurrence of X1, R3, or Q1 may be the same or different; or a combination comprising at least one of the foregoing co-monomers. ### Claim 32 (depends on 19) The electrochromic device of claim 19, wherein the first conjugated polymer has been doped with a p-dopant or an n-dopant. ### Claim 33 (depends on 19) The electrochromic device of claim 19, wherein the first and second electrodes are glass-indium doped tin oxide (glass-ITO). ### Claim 34 (depends on 19) The electrochromic device of claim 19, wherein the electrolyte layer is a gel electrolyte comprising lithium trifluomethanesulfonate, lithium trifluoromethanesulfonimide, tetraalkylammonium hexafluorophosphates, tetraalkylammonium tosylates, or N-alkylimmidazoliunium salts dissolved in a polymer matrix, wherein the polymatrix is a poly(meth)acrylic, a polystyrenic, or a homopolymer or copolymer of polyethyleneglycol; and wherein the gel electrolyte is optionally plasticized. ### Claim 35 An electrochromic device, comprising: a substantially transparent outer layer; a first electrode located behind the transparent outer layer, wherein the first electrode comprises a reflective surface facing the outer layer and a means for allowing ions to pass through the first electrode; a first layer comprising a first conjugated polymer disposed between the reflective surface and the transparent outer layer and in electrical communication with the first electrode, wherein the first conjugated polymer is an electrochromic material; a first electrolyte layer in contact with the first layer and the first electrode; a second electrode located behind the transparent outer layer and behind the first electrode; a second layer comprising a second conjugated polymer, wherein the second conjugated polymer has a band gap of less than or equal to about 1.5 eV and an Lmax absorption peak of greater than or equal to about 750 nm in the neutral, oxidized, and reduced forms, wherein the second layer is disposed on and in electrical communication with the second electrode; and a second electrolyte layer disposed between the second layer and the first electrode.