# US 10,504,660 B2 · Sensitizing dye solution, working electrode for dye-sensitized solar cell prepared using the sensitizing dye solution and dye-sensitized solar cell including the working electrode > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,504,660 B2 - Document ID: US10504660B2 - Status: Granted - Kind: B2 - Application number: 14/511,656 - Filed: 2014-10-10 - Published: 2015-12-24 - Granted: 2019-12-10 - Earliest claimed: 2014-06-18 - Assignees: Korean Institute of Science and Technology - Applicants: Korea Institute of Science and Technology - Inventors: Min Jae Ko; Bong Soo Kim; Jin Young Kim; Hong Gon Kim; Hae Jung Son; Doh-Kwon Lee; Jin Ah Lee; Hee Suk Jung; Hwa Young Jin - Web page: https://patentgrep.com/patent/US10504660B2 ## CPC - H01G 9/2059: {comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution} - H10K 85/344: {comprising ruthenium} - H01G 9/2031: {comprising titanium oxide, e.g. TiO2 (H01G9/2036 takes precedence)} - Y02E 10/542: Dye sensitized solar cells - Y02E 10/549: Organic PV cells - H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10) - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract Disclosed is a method for adsorbing a dye for a dye-sensitized solar cell. The method includes: coating a paste including metal oxide nanoparticles on the upper surface of a titanium oxide thin film and calcining the coated paste to form a porous film; adding an additive to a sensitizing dye solution to promote the adsorption of the dye; and dipping the porous film in the sensitizing dye solution to adsorb the sensitizing dye onto the surface of the porous film. The sensitizing dye solution is a dispersion of the sensitizing dye in an organic solvent. Also disclosed are a working electrode prepared using the sensitizing dye solution and a dye-sensitized solar cell including the working electrode. The addition of the additive shortens the time of dye adsorption. Despite the shortened adsorption time, the dye does not undergo desorption in the long term as well as in the short term, ensuring long-term stability of the solar cell. ## Claims ### Claim 1 A sensitizing dye solution for the preparation of a working electrode of a dye-sensitized solar cell, comprising a sensitizing dye, an organic solvent, and an additive wherein the additive is a mixture of (i) a first additive selected from diphenylammonium trifluoromethanesulfonate (DPAT), pentafluoroanilinium triflate (PFPAT), pentafluorophenylammonium trifluoromethanesulfonate, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, 4-methylbenzenesulfonic acid, (7,7-dimethyl-2-oxobicyclo[2,2,1]-hept-1-yl)methanesulfonic acid, and mixtures of two or more thereof, and (ii) a second additive selected from hydrochloric acid, phosphoric acid, acetic acid, nitric acid, and mixtures of two or more thereof, wherein the contents of the first additive and the second additive are from 1.5 to 10 moles and from 1.5 to 10 moles, respectively, based on one mole of the sensitizing dye, and the molar ratio of the first additive to the second additive is from 99:1 to 80:20 wherein the additive improves the rate of adsorption of the sensitizing dye to titanium oxide. ### Claim 2 (depends on 1) The sensitizing dye solution according to claim 1, wherein the sensitizing dye has a band gap of 1.55 to 3.1 eV. ### Claim 3 (depends on 1) The sensitizing dye solution according to claim 1, wherein the sensitizing dye is selected from an organic-inorganic complex dye comprising a metal or metal complex, an organic dye, and a mixture thereof. ### Claim 4 (depends on 3) The sensitizing dye solution according to claim 3, wherein the organic-inorganic complex dye is selected from ruthenium (Ru) complex dyes, osmium (Os) complex dyes, platinum (Pt) complex dyes, copper (Cu) complex dyes, porphyrin complex dyes, phthalocyanine complex dyes, and mixtures of two or more thereof. ### Claim 5 (depends on 3) The sensitizing dye solution according to claim 3, wherein the organic dye is selected from coumarin-based organic dyes, indoline-based organic dyes, carbazole-based organic dyes, triarylamine-based organic dyes, perylene-based organic dyes, hemicyanine-based organic dyes, squaraine-based organic dyes, and mixtures of two or more thereof. ### Claim 6 (depends on 1) The sensitizing dye solution according to claim 1, wherein the organic solvent is selected from ethanol, acetonitrile, tetrahydrofuran, dimethyl chloride, and mixtures of two or more thereof. ### Claim 7 (depends on 1) A method for preparing a working electrode of a dye-sensitized solar cell, the method comprising (C) bringing the sensitizing dye solution according to claim 1 into contact with a porous substrate wherein the porous substrate comprises a titanium oxide thin film and a 10 nm to 30 μm thick porous film formed on the upper surface of the titanium oxide thin film. ### Claim 8 (depends on 1) A method for preparing a working electrode of a dye-sensitized solar cell, the method comprising (B) forming a porous film on the upper surface of a titanium oxide thin film formed on a transparent conductive substrate to obtain a porous substrate, and (C) bringing the sensitizing dye solution according to claim 1 into contact with the porous substrate. ### Claim 9 (depends on 1) A method for preparing a working electrode of a dye-sensitized solar cell, the method comprising (A) forming a titanium oxide thin film on a transparent conductive substrate, (B) forming a porous film on the upper surface of the titanium oxide thin film to obtain a porous substrate, and (C) bringing the sensitizing dye solution according to claim 1 into contact with the porous substrate. ### Claim 10 (depends on 9) The method according to claim 9, wherein step (A) is carried out by (i) coating a titanium oxide precursor on a transparent conductive substrate, followed by heat treatment, or (ii) forming a conductive film on one surface of a transparent substrate, coating a titanium oxide precursor on the conductive film, followed by heat treatment. ### Claim 11 (depends on 10) The method according to claim 10, wherein the heat treatment is performed at 100 to 600° C. ### Claim 12 (depends on 8) The method according to claim 8, wherein the titanium oxide thin film is from 50 to 250 nm in thickness. ### Claim 13 (depends on 8) The method according to claim 8, wherein step (B) is carried out by coating a paste comprising metal oxide nanoparticles on the upper surface of the titanium oxide thin film and calcining the coated paste. ### Claim 14 (depends on 13) The method according to claim 13, wherein the metal oxide is selected from tin (Sn) oxide, antimony (Sb) oxide, niobium (Nb) oxide, fluorine-doped tin (Sn) oxide, indium (In) oxide, tin-doped indium (In) oxide, zinc (Zn) oxide, aluminum (Al) oxide, boron (B) oxide, gallium (Ga) oxide, hydrogen (H) oxide, yttrium (Y) oxide, titanium (Ti) oxide, silicon (Si)-doped zinc (Zn) oxide, tin (Sn)-doped zinc (Zn) oxide, magnesium (Mg) oxide, cadmium (Cd) oxide, magnesium zinc (MgZn) oxide, indium zinc (InZn) oxide, copper aluminum (CuAl) oxide, silver (Ag) oxide, zinc tin oxide (ZnSnO), zinc indium tin (ZIS) oxide, nickel (Ni) oxide, rhodium (Rh) oxide, ruthenium (Ru) oxide, iridium (Ir) oxide, copper (Cu) oxide, cobalt (Co) oxide, tungsten (W) oxide, zirconium (Zr) oxide, strontium (Sr) oxide, lanthanum (La) oxide, vanadium (V) oxide, molybdenum (Mo) oxide, scandium (Sc) oxide, samarium (Sm) oxide, strontium titanium (SrTi) oxide, and mixtures of two or more thereof. ### Claim 15 (depends on 13) The method according to claim 13, wherein the metal oxide nanoparticles have an average particle diameter of 10 to 100 nm. ### Claim 16 (depends on 13) The method according to claim 13, wherein the paste further comprises a binder and a solvent. ### Claim 17 (depends on 7) The method according to claim 7, wherein the calcination is performed at 100 to 600° C. for 30 to 200 minutes. ### Claim 18 (depends on 7) The method according to claim 7, wherein the porous film has a thickness of 10 nm to 30 μm. ### Claim 19 (depends on 7) The method according to claim 7, wherein step (C) is carried out by (i) dipping the porous substrate in the sensitizing dye solution, (ii) spraying the sensitizing dye solution on the porous substrate, or (iii) dropping the sensitizing dye solution onto the porous substrate. ### Claim 20 (depends on 19) The method according to claim 19, wherein the porous film is dipped in the sensitizing dye solution at 30 to 50° C. for 1 to 180 minutes. ### Claim 21 (depends on 7) A working electrode for a dye-sensitized solar cell prepared by the method according to claim 7. ### Claim 22 (depends on 7) A dye-sensitized solar cell comprising (a) a working electrode prepared by the method according to claim 7, (b) a counter electrode arranged to face the working electrode and comprising a catalyst layer, and (c) an electrolyte filled between the working electrode and the counter electrode.