CN111681879A - Non-platinum-based transparent electrode material and preparation method and application thereof - Google Patents

Non-platinum-based transparent electrode material and preparation method and application thereof Download PDF

Info

Publication number
CN111681879A
CN111681879A CN202010690481.9A CN202010690481A CN111681879A CN 111681879 A CN111681879 A CN 111681879A CN 202010690481 A CN202010690481 A CN 202010690481A CN 111681879 A CN111681879 A CN 111681879A
Authority
CN
China
Prior art keywords
platinum
based transparent
electrode material
transparent electrode
molybdenum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010690481.9A
Other languages
Chinese (zh)
Other versions
CN111681879B (en
Inventor
王莹琳
张昕彤
李蓉
林峻
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University China
Northeast Normal University
Original Assignee
Northeast Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeast Normal University filed Critical Northeast Normal University
Priority to CN202010690481.9A priority Critical patent/CN111681879B/en
Publication of CN111681879A publication Critical patent/CN111681879A/en
Application granted granted Critical
Publication of CN111681879B publication Critical patent/CN111681879B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention provides a non-platinum-based transparent electrode material and a preparation method and application thereof, belonging to the technical field of solar cells. The non-platinum-based transparent electrode material provided by the invention comprises an FTO substrate, a molybdenum-based transparent conductive carrier film positioned on the surface of the FTO substrate and non-platinum transition metal positioned on the surface of the molybdenum-based transparent conductive carrier film; the particle size of the non-platinum transition metal is less than or equal to 5 nm; the thickness of the molybdenum-based transparent conductive carrier film is 5-30 nm. The non-platinum-based transparent electrode material provided by the invention takes FTO as a substrate, and has high transparency; the molybdenum-based transparent conductive carrier film has good uniformity and permeability, and can improve the dispersion uniformity of non-platinum transition metal; the non-platinum transition metal has small particle size and large specific surface area, and ensures high catalytic activity of the non-platinum-based transparent electrode material. The non-platinum-based transparent electrode material provided by the invention has high transmittance, and can meet the requirements of laminated, double-sided irradiation and transparent photoelectric devices on electrodes.

Description

Non-platinum-based transparent electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a non-platinum-based transparent electrode material and a preparation method and application thereof.
Background
Dye-sensitized solar cells (DSCs) have rich appearance colors, high transparency and low efficiency affected by incident light, so that the DSCs have wide marketable application prospects in laminated, double-sided irradiation and transparent photoelectric devices. The counter electrode can play a role in promoting the reduction of the electrolyte and is an important component of the DSCs. With the continuous development of science and technology, higher requirements are put forward on counter electrodes of DSCs, for example, the counter electrodes need to meet the requirements of high conductivity, high catalytic activity, high transparency, easy preparation, low cost and the like. Currently, a common counter electrode for DSCs is a noble metal platinum (Pt) electrode, however, a Pt electrode obtained by pyrolyzing chloroplatinic acid at 450 ℃ has a low transmittance (< 55%) in a visible light region, and a Pt material is expensive, so that the manufacturing cost of the counter electrode accounts for more than 60% of the whole battery.
Disclosure of Invention
In view of the above, the present invention provides a non-platinum-based transparent electrode material, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a non-platinum-based transparent electrode material, which comprises an FTO substrate, a molybdenum-based transparent conductive carrier film positioned on the surface of the FTO substrate and non-platinum transition metal positioned on the surface of the molybdenum-based transparent conductive carrier film; the particle size of the non-platinum transition metal is less than or equal to 5 nm; the thickness of the molybdenum-based transparent conductive carrier film is 5-30 nm.
Preferably, the non-platinum transition metal comprises cobalt, nickel, copper or iron.
Preferably, the material of the molybdenum-based transparent conductive carrier film comprises Mo2C or MoO3。
The invention provides a preparation method of the non-platinum-based transparent electrode material in the technical scheme, which comprises the following steps:
performing magnetron sputtering on the surface of the FTO substrate by taking a molybdenum-based conductive carrier as a target to obtain an FTO-molybdenum-based transparent conductive carrier film;
and placing the FTO-molybdenum-based transparent conductive carrier membrane into a non-platinum transition metal salt solution for dipping, and calcining under a protective atmosphere to obtain the non-platinum-based transparent electrode material.
Preferably, the working parameters of magnetron sputtering include: the reaction gas is argon, the pressure is 0.6-0.8 Pa, the power is 60-80W, the temperature is 20-300 ℃, and the time is 0.5-3 min.
Preferably, the non-platinum transition metal salt in the non-platinum transition metal salt solution comprises a cobalt salt, a nickel salt, a copper salt or an iron salt;
the concentration of the non-platinum transition metal salt solution is 5-20 mmol/L.
Preferably, the dipping temperature is room temperature, and the time is 3-5 h.
Preferably, the calcining temperature is 400-500 ℃, the heating rate of heating to the calcining temperature is 400-450 ℃/min, and the heat preservation time is 10-15 min.
The invention provides an application of the non-platinum-based transparent electrode material in the technical scheme or the non-platinum-based transparent electrode material prepared by the preparation method in the technical scheme in a dye-sensitized solar cell.
The invention provides a non-platinum-based transparent electrode material, which comprises an FTO substrate, a molybdenum-based transparent conductive carrier film positioned on the surface of the FTO substrate and non-platinum transition metal positioned on the surface of the molybdenum-based transparent conductive carrier film; the particle size of the non-platinum transition metal is less than or equal to 5 nm; the thickness of the molybdenum-based transparent conductive carrier film is 5-30 nm. The invention provides a non-platinum-based transparent electrode material which is prepared from FTO (fluorine-doped SnO)2Conductive glass) as a substrate, the transparency is high; the molybdenum-based transparent conductive carrier membrane is thin, has good uniformity and permeability, and can improve the dispersion uniformity of non-platinum transition metal on the surface of the molybdenum-based transparent conductive carrier membrane and improve the catalytic activity of the non-platinum-based transparent electrode material; the non-platinum transition metal has small particle size and large specific surface area, so that the high catalytic activity of the non-platinum-based transparent electrode material is ensured; the non-platinum-based transparent electrode material provided by the invention can maintain the transmittance of a visible light region of an FTO (fluorine-doped tin oxide) substrate97.7 percent of the total reflection area, high transmittance and capability of meeting the requirements of laminated, double-sided irradiation and transparent photoelectric devices on electrodes.
The invention provides a preparation method of the non-platinum-based transparent electrode material, which comprises the following steps: performing magnetron sputtering on the surface of the FTO substrate by taking a molybdenum-based conductive carrier as a target to obtain an FTO-molybdenum-based transparent conductive carrier film; and placing the FTO-molybdenum-based transparent conductive carrier membrane into a non-platinum transition metal salt solution for dipping, and calcining under a protective atmosphere to obtain the non-platinum-based transparent electrode material. The method for preparing the molybdenum-based transparent conductive carrier film by using the magnetron sputtering method can realize the control of the thickness of the molybdenum-based transparent conductive carrier film and improve the transparency of the electrode material. The preparation method provided by the invention is simple to operate, low in cost and suitable for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of a non-platinum-based transparent electrode material prepared in example 1;
FIG. 2 is an elemental distribution diagram of the non-platinum-based transparent electrode material prepared in example 1, wherein OK is an oxygen elemental distribution diagram, CK is a carbon elemental distribution diagram, Mo L is a molybdenum elemental distribution diagram, and Co L is a cobalt elemental distribution diagram;
FIG. 3 is a graph showing transmittance of the non-platinum transparent electrode materials prepared in examples 1, 4 to 6;
fig. 4 is a graph showing transmittance of an FTO substrate, a non-platinum-based transparent electrode material prepared in example 1, and a Pt electrode prepared in comparative example 1;
FIG. 5 is an optical photograph of a large-area transparent counter electrode having a size of 5cm × 5cm prepared in example 1;
FIG. 6 is a Taffeta polarization plot of the non-platinum based transparent electrode materials prepared in examples 1 and 7;
FIG. 7 is a Taffeta polarization curve of the non-platinum-based transparent electrode materials prepared in examples 1, 4-6;
FIG. 8 is a Taffer polarization plot of a non-platinum based transparent electrode material prepared in example 1 and a Pt electrode prepared in comparative example 1;
fig. 9 is an electrochemical impedance spectrum of a non-platinum-based transparent electrode material prepared in example 1, and a Pt electrode prepared in comparative example 1;
fig. 10 is a graph showing front and back side irradiation current-voltage characteristics of DSCs based on the non-platinum based transparent electrode material prepared in example 1 and the Pt electrode prepared in comparative example 1;
fig. 11 is a schematic view of a current-voltage curve of a solar cell.
Detailed Description
The invention provides a non-platinum-based transparent electrode material, which comprises an FTO substrate, a molybdenum-based transparent conductive carrier film positioned on the surface of the FTO substrate and non-platinum transition metal positioned on the surface of the molybdenum-based transparent conductive carrier film; the particle size of the non-platinum transition metal is less than or equal to 5 nm; the thickness of the molybdenum-based transparent conductive carrier film is 5-30 nm.
In the invention, the thickness of the FTO substrate is preferably 1-3 mm, more preferably 1.5-2.5 mm, and most preferably 2-2.2 mm.
In the present invention, the material of the molybdenum-based transparent conductive carrier film preferably comprises Mo2C or MoO3. In the present invention, the Mo is2C and MoO3The purity of (A) is independently preferably 99.99% or more. In the invention, the thickness of the molybdenum-based transparent conductive carrier film is 5-30 nm, preferably 10-25 nm, and more preferably 15-20 nm.
In the present invention, the non-platinum transition metal preferably includes cobalt, nickel, copper or iron. In the invention, the particle size of the non-platinum transition metal is less than or equal to 5 nm. In the present invention, the non-platinum transition metal is preferably distributed in the form of nanoclusters on the surface of the molybdenum-based transparent conductive support membrane.
The invention provides a preparation method of the non-platinum-based transparent electrode material in the technical scheme, which comprises the following steps:
performing magnetron sputtering on the surface of the FTO substrate by taking a molybdenum-based conductive carrier as a target to obtain an FTO-molybdenum-based transparent conductive carrier film;
and placing the FTO-molybdenum-based transparent conductive carrier membrane into a non-platinum transition metal salt solution for dipping, and calcining under a protective atmosphere to obtain the non-platinum-based transparent electrode material.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention takes a molybdenum-based conductive carrier as a target material to carry out magnetron sputtering on the surface of the FTO substrate to obtain the FTO-molybdenum-based transparent conductive carrier film.
The size of the FTO substrate is not particularly limited and is preferably adjusted according to actual needs, in the embodiment of the invention, the size of the FTO substrate is preferably (1-6) cm × (1-6) cm, and more preferably (1.5-5) cm × (1.5-5) cm.. in the invention, the FTO substrate is preferably used and further comprises pretreatment, the pretreatment preferably comprises sequential cleaning and washing, acetone washing, ethanol washing, drying and ultraviolet ozone irradiation treatment, in the invention, the cleaning and washing, the acetone washing and the ethanol washing are preferably carried out under ultrasonic conditions, the power of ultrasonic waves is not particularly limited, ultrasonic power well known by persons skilled in the art is adopted, the time of the cleaning and washing, the acetone washing and the ethanol washing are independently preferably 10-20 min, more preferably 15min, the drying mode is preferably blow drying, in the invention, the ultraviolet ozone irradiation treatment is preferably carried out by a UV light ozone cleaning machine, and the power of the ultraviolet irradiation ozone treatment is preferably 30-20 cm/mW/20/mW/cm2More preferably 25mW/cm2(ii) a The wavelength of ultraviolet light irradiated by the ultraviolet ozone is preferably 185-254 nm; the time of the ultraviolet ozone irradiation treatment is preferably 10-20 min, and more preferably 15 min. In the invention, the organic pollutant impurities on the surface of the FTO substrate can be removed through the pretreatment.
In the present invention, the target preferably includes Mo2C target or MoO3A target. In the present invention, the Mo is2C target and MoO3The purity of the target is preferably 99.99% or more, independently.
In the invention, the magnetron sputtering is carried out in a magnetron sputtering chamber; the method is characterized by further comprising the steps of fixing a target material, closing the target material baffle and the substrate baffle, then carrying out pre-magnetron sputtering, opening the target material baffle and the substrate baffle after the pre-magnetron sputtering is finished, and carrying out magnetron sputtering on the FTO substrate. In the present invention, the operating parameters of the pre-magnetron sputtering include: the reaction gas is preferably argon; the pressure of the reaction gas is preferably 0.6-0.8 Pa, more preferably 0.65-0.75 Pa, and most preferably 0.7 Pa; the power of the pre-magnetron sputtering is preferably 60-80W, more preferably 65-75W, and most preferably 70W; the temperature of the pre-magnetron sputtering is preferably 20-300 ℃, more preferably 50-250 ℃, and most preferably 100-200 ℃; the time of the pre-magnetron sputtering is preferably 5-30 min, more preferably 10-25 min, and most preferably 15-25 min. In the invention, the pre-magnetron sputtering can further remove impurities on the surface of the molybdenum-based conductive carrier target material, thereby improving the purity of the obtained molybdenum-based transparent conductive carrier film.
In the invention, the working parameters of magnetron sputtering include: the reaction gas is preferably argon; the pressure of the reaction gas is preferably 0.6-0.8 Pa, more preferably 0.65-0.75 Pa, and most preferably 0.7 Pa; the magnetron sputtering power is preferably 60-80W, more preferably 65-75W, and most preferably 70W; the magnetron sputtering temperature is preferably 20-300 ℃, more preferably 50-250 ℃, and most preferably 100-200 ℃; the time of the magnetron sputtering is preferably 0.5-3 min, more preferably 1-2.5 min, and most preferably 1.5-2.5 min.
After the magnetron sputtering, the invention preferably further comprises the step of cooling the product after the magnetron sputtering to room temperature to obtain the FTO-molybdenum-based transparent conductive carrier film. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used.
After the FTO-molybdenum-based transparent conductive carrier membrane is obtained, the FTO-molybdenum-based transparent conductive carrier membrane is placed in a non-platinum transition metal salt solution for dipping and then is calcined under a protective atmosphere to obtain the non-platinum-based transparent electrode material.
In the present invention, the non-platinum transition metal salt in the non-platinum transition metal salt solution preferably includes a cobalt salt, a nickel salt, a copper salt, or an iron salt; the cobalt salt preferably comprises cobalt nitrate or cobalt chloride; the nickel salt preferably comprises nickel nitrate or nickel chloride; the copper salt preferably comprises copper nitrate or copper chloride; the iron salt preferably comprises ferric nitrate or ferric chloride. In the present invention, the solvent in the non-platinum transition metal salt solution preferably includes ultrapure water, absolute ethanol, or isopropanol. In the present invention, the non-platinum transition metal salt solution is preferably an aqueous cobalt nitrate solution, an ethanol cobalt nitrate solution, an isopropanol cobalt nitrate solution, an aqueous cobalt chloride solution, an ethanol cobalt chloride solution, an isopropanol cobalt chloride solution, an aqueous nickel nitrate solution, an ethanol nickel nitrate solution, an isopropanol nickel nitrate solution, an aqueous nickel chloride solution, an ethanol nickel chloride solution, an isopropanol nickel chloride solution, an aqueous copper nitrate solution, an aqueous copper chloride solution, an ethanol copper chloride solution, an isopropanol copper chloride solution, an aqueous ferric nitrate solution, an ethanol ferric nitrate solution, an isopropanol ferric chloride solution, an aqueous ferric chloride solution, or an isopropanol ferric chloride solution. In the invention, the concentration of the non-platinum transition metal salt solution is preferably 5-20 mmol/L, more preferably 8-18 mmol/L, and most preferably 10-15 mmol/L. The dosage of the non-platinum transition metal salt solution is not particularly limited, and the molybdenum-based transparent conductive carrier membrane can be immersed.
In the present invention, the non-platinum transition metal salt solution is preferably prepared as it is, and the preparation method of the non-platinum transition metal salt solution preferably includes the steps of: mixing the non-platinum transition metal salt and the solvent to obtain the non-platinum transition metal salt solution. In the present invention, the mixing is preferably stirring mixing, and the speed and time of the stirring mixing are not particularly limited, and the non-platinum transition metal salt may be completely dissolved in the solvent.
In the present invention, the temperature of the impregnation is preferably room temperature; the time is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and most preferably 4 hours. In the invention, the impregnation is preferably carried out under a sealed condition, and the impregnation is carried out under a sealed condition, so that the influence of oxygen in the air can be avoided as much as possible, and the volatilization of a solvent in a non-platinum transition metal salt solution can be reduced. In the invention, in the impregnation process, non-platinum transition metal ions are loaded on the surface of the molybdenum-based transparent conductive carrier membrane through electrostatic adsorption.
After the impregnation, the present invention preferably further comprises sequentially washing and drying the impregnated product. In the present invention, the water washing is preferably water washing, and the time of the water washing is not particularly limited in the present invention, and the non-platinum transition metal salt solution on the surface of the impregnated product may be washed clean. In the present invention, the drying is preferably blow drying, which is preferably performed using an air gun.
The protective atmosphere in the present invention is not particularly limited, and a protective atmosphere known to those skilled in the art may be used, specifically, nitrogen. In the invention, the calcination temperature is preferably 400-500 ℃, more preferably 420-480 ℃, and most preferably 450-460 ℃; the heating rate of the temperature rising to the calcining temperature is preferably 400-450 ℃/min, more preferably 410-440 ℃/min, and most preferably 420-430 ℃/min; the heat preservation time is preferably 10-15 min, more preferably 11-14 min, and most preferably 12-13 min. In the present invention, during the calcination process, the non-platinum transition metal salt is thermally decomposed to obtain non-platinum transition metal particles.
After the calcination, the invention preferably further comprises cooling the calcined product to room temperature to obtain the non-platinum-based transparent electrode material. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used.
The invention provides an application of the non-platinum-based transparent electrode material in the technical scheme or the non-platinum-based transparent electrode material prepared by the preparation method in the technical scheme in a dye-sensitized solar cell.
In the present invention, the composition of the dye-sensitized solar cell is: the photo-anode is a porous membrane loaded with dye, the electrolyte is redox electrolyte, and the non-platinum-based transparent electrode material is a counter electrode.
In the present invention, the dye preferably includes an N719 dye or a Y123 dye. In the present invention, the porous film preferably comprises TiO2。
In the present invention, the method for preparing the photo-anode preferably comprises the steps of:
(1) placing the FTO in a metal salt aqueous solution for soaking, then carrying out first heat preservation and first drying to obtain a pretreated FTO;
(2) coating the porous membrane slurry on the surface of the pretreated FTO, soaking in a metal salt aqueous solution, and then carrying out second heat preservation and second drying to obtain a porous membrane;
(3) and annealing the porous membrane and soaking the porous membrane in a dye solution to obtain the photo-anode.
The method comprises the steps of soaking pretreated FTO in a metal salt aqueous solution, preserving heat and drying to obtain pretreated FTO.
In the present invention, the FTO is preferably pretreated during the lifetime, and the pretreatment method is preferably the same as the pretreatment method for the FTO substrate in the preparation process of the non-platinum-based transparent electrode material, and is not described herein again.
In the present invention, the metal in the aqueous metal salt solution in the steps (1) and (2) is preferably the same as the metal in the porous film, and more preferably TiCl4An aqueous solution; the concentration of the aqueous metal salt solution is preferably 30 to 50mmol/L, more preferably 35 to 45mmol/L, and most preferably 40 mmol/L.
In the invention, the temperature of the first heat preservation is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 70 ℃; the time is preferably 20 to 40min, more preferably 25 to 35min, and most preferably 30 min.
In the present invention, the first drying method is preferably blow drying.
After the pre-treatment FTO is obtained, the porous membrane slurry is coated on the surface of the pre-treatment FTO, and the porous membrane slurry is soaked in a metal salt aqueous solution, and then subjected to secondary heat preservation and secondary drying to obtain the porous membrane.
In the present invention, the coating is preferably screen printing knife coating.
In the invention, the temperature of the second heat preservation is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 70 ℃; the time is preferably 10 to 30min, more preferably 15 to 25min, and most preferably 20 min.
In the present invention, the first drying method is preferably blow drying.
In the present invention, the thickness of the porous film is preferably 9 to 13 μm, more preferably 10 to 12 μm, and most preferably 11 μm. The invention controls the thickness of the porous membrane within the range, which is beneficial to the dye to fully absorb sunlight and increase the utilization rate of the sunlight.
After the porous membrane is obtained, the porous membrane is annealed and then soaked in a dye solution to obtain the photo-anode.
In the invention, the annealing temperature is preferably 450-550 ℃, more preferably 480-520 ℃, and most preferably 500 ℃; the time is preferably 20 to 40min, more preferably 25 to 35min, and most preferably 30 min. In the present invention, the annealing is preferably performed in a resistance furnace.
After said annealing, the invention preferably further comprises cooling. In the invention, the temperature after cooling is preferably 90-100 ℃, more preferably 95-105 ℃, and most preferably 100 ℃. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used.
In the present invention, the dye solution preferably includes a N719 dye solution or a Y123 dye solution; the concentration of the dye solution is preferably 280-320 mu mol/L, more preferably 290-310 mu mol/L, and most preferably 300 mu mol/L.
In the invention, the soaking time is preferably 22-26 h, more preferably 23-25 h, and most preferably 24 h.
After said soaking, the present invention preferably further comprises taking out the material and drying it. In the present invention, the drying is preferably performed by blow drying.
In the present invention, the redox electrolyte preferably comprises I-/I3 -Redox electrolyte or [ Co (phen)3]3+/2+Redox electrolyte of said I-/I3 -The composition of the solution of the redox electrolyte is preferably 1, 3-dimethyl imidazole iodonium salt, guanidine thiocyanate, iodine simple substance, lithium iodide, 4-tert-butylpyridine and solvent; the concentration of the 1, 3-dimethyl imidazole iodonium salt is preferably 0.4-0.8 mol/L, more preferably 0.5-0.7 mol/L, and most preferably 0.6 mol/L; the concentration of the guanidine thiocyanate is preferably 0.05-0.2 mol/L, and more preferably 0.05-0.2 mol/L0.1-0.15 mol/L, most preferably 0.1 mol/L; the concentration of the iodine simple substance is preferably 0.01-0.05 mol/L, more preferably 0.02-0.04 mol/L, and most preferably 0.03 mol/L; the concentration of the lithium iodide is preferably 0.04-0.06 mol/L, more preferably 0.045-0.055 mol/L, and most preferably 0.05 mol/L; the concentration of the 4-tert-butylpyridine is preferably 0.3-0.7 mol/L, more preferably 0.4-0.6 mol/L, and most preferably 0.5 mol/L; the solvent is preferably a mixed solvent of acetonitrile and valeronitrile, and the volume ratio of the acetonitrile to the valeronitrile is preferably (83-87): (13-17), more preferably (84-86): (14-16), and most preferably 85: 15.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ultrasonically cleaning an FTO substrate with the thickness of 2.2mm in liquid detergent, acetone and ethanol for 15min respectively, taking out the FTO substrate, drying the FTO substrate, and carrying out ultraviolet ozone irradiation treatment for 15min to obtain a pretreated FTO substrate;
placing the pretreated FTO substrate in a magnetron sputtering chamber, and fixing Mo2C, closing the target baffle and the substrate baffle, performing magnetron sputtering for 5min in advance, opening the target baffle and the substrate baffle, performing magnetron sputtering for 2min on the FTO substrate to be pretreated, and cooling to room temperature to obtain Mo with the thickness of about 15nm2C a conductive carrier film; the working parameters of the pre-magnetron sputtering and the magnetron sputtering are as follows: argon is used as reaction gas, the pressure of the reaction gas is 0.8Pa, the power is 60W, and the temperature is 200 ℃;
0.0436g of Co (NO)3)2·6H2O and 15mL of ultrapure water are stirred and mixed for 15min to obtain a cobalt nitrate aqueous solution (the concentration is 10 mmol/L); mixing the Mo2Soaking the C conductive carrier membrane in cobalt nitrate water solution at room temperature under a sealed condition for 3h, washing with water, blowing with an air gun, and heating to 430 deg.C/min under the protection of nitrogenCalcining at 450 deg.C for 10min to obtain non-platinum transparent electrode material (Co-Mo2C)。
Co-Mo prepared in this example2Scanning Electron Microscope (SEM) of C As shown in FIG. 1, the FTO surface morphology clearly seen in FIG. 1, no other signals, illustrates the Mo carrier2The particles of C and supported metal Co are both small (less than 10 nm).
Co-Mo prepared in this example2The Mapping diagram of C is shown in FIG. 2, wherein O K is the diagram of oxygen element, C K is the diagram of carbon element, Mo L is the diagram of molybdenum element, and Co L is the diagram of cobalt element. From FIG. 2, it can be seen that there are significant Mo and Co element signals, and they are uniformly dispersed on FTO, which shows that Co is uniformly loaded on Mo2C on a conductive carrier.
Example 2
A non-platinum-based transparent electrode material was prepared in the same manner as in example 1, except that the aqueous cobalt nitrate solution was replaced with an ethanol solution of cobalt nitrate.
Example 3
A non-platinum-based transparent electrode material was prepared in the same manner as in example 1, except that the aqueous cobalt nitrate solution was replaced with an isopropyl alcohol solution of cobalt nitrate.
Example 4
A non-platinum-based transparent electrode material was prepared according to the method of example 1, except that Co (NO) was used3)2·6H2Replacement of O by Ni (NO)3)2·6H2O, the concentration of the nickel nitrate aqueous solution is 10 mmol/L; obtaining a non-platinum-based transparent electrode material (abbreviated as Ni-Mo)2C)。
Example 5
A non-platinum-based transparent electrode material was prepared according to the method of example 1, except that 0.0436g of Co (NO) was used3)2·6H2Replacement of O by 0.0362g Cu (NO)3)2·3H2O, the concentration of the copper nitrate aqueous solution is 10 mmol/L; obtaining a non-platinum-based transparent electrode material (Cu-Mo for short)2C)。
Example 6
A non-platinum-based transparent electrode material was prepared according to the method of example 1, except that 0.0436g of Co (NO) was used3)2·6H2O is replaced by 0.0606gFe (NO)3)2·9H2O, the concentration of the ferric nitrate aqueous solution is 10 mmol/L; obtaining a non-platinum-based transparent electrode material (abbreviated as Fe-Mo)2C)。
Example 7
A non-platinum-based transparent electrode material was prepared according to the method of example 1, except that Mo was added to the solution of example 12C target material is replaced by MoO3Target material to obtain MoO3Conductive carrier film, the resulting non-platinum based transparent electrode material being abbreviated as Co-MoO3。
Comparative example 1
H with the purity of 99.7 percent2PtCl6·6H2Dissolving O in an isopropanol solvent, and uniformly stirring to obtain a chloroplatinic acid isopropanol solution with the concentration of 10 mmol/L;
ultrasonically cleaning an FTO substrate with the thickness of 2.2mm in liquid detergent, acetone and ethanol for 15min respectively, taking out the FTO substrate, drying the FTO substrate, and carrying out ultraviolet ozone irradiation treatment for 15min to obtain a pretreated FTO substrate;
and (3) placing the pretreated FTO substrate on a spin coater sucker, vacuumizing and fixing, spin-coating for 3s at 700r/min, accelerating to 1500r/min for spin-coating for 30s, dropwise adding 50 mu L of chloroplatinic acid isopropanol solution for spin-coating, heating on a hot plate at 450 ℃ for 10min, cooling to room temperature, and repeating the operation for 5 times to obtain the platinum electrode material (abbreviated as Pt).
Test example
(1) Transmittance test
As shown in FIG. 3 and Table 1, the transmittances of the non-platinum-based transparent electrode materials prepared in examples 1, 4 to 6, FTO substrates, and Co-Mo prepared in example 12The permeability of Pt prepared in C and comparative example 1 is shown in fig. 4 and table 1; Co-Mo prepared in example 12The optical photograph of C is shown in fig. 5.
TABLE 1 permeability of FTO substrates, electrodes prepared in examples 1, 4-6 and comparative example 1
Figure BDA0002589173260000111
As can be seen from Table 1 and FIGS. 3 to 4, Co-Mo prepared by the present invention2C、Ni-Mo2C、Cu-Mo2C and Fe-Mo2C has high transmittance in a visible light range, and the transmittance is reduced by about 2% relative to that of the FTO substrate; Co-Mo prepared in example 12The transmittance of the Pt electrode prepared by the method C is obviously improved compared with that of the Pt electrode prepared by the comparative example 1; the Co-Mo prepared in example 1 can also be seen from FIG. 52C has excellent optical transmittance.
(2) Electrocatalytic performance test
The taffy polarization curves of the non-platinum-based transparent electrode materials prepared in examples 1 and 7 are shown in fig. 6, the taffy polarization curves of the non-platinum-based transparent electrode materials prepared in examples 1 and 4-6 are shown in fig. 7, and the intersection point of the tangent line of the cathode branch of the taffy region and the equilibrium potential in the taffy polarization curve is the exchange current density J0，J0The higher the electrode electrocatalysis effect is, the better the electrode electrocatalysis effect is; as can be seen from FIG. 6, Mo is used2The electrocatalytic activity of the non-platinum-based transparent electrode material with the carrier C is higher; as can be seen from FIG. 7, the electrocatalytic activities of the electrode materials of different non-platinum transition metals are slightly different, wherein the catalytic activities are Co-Mo in sequence2C＞Cu-Mo2C＞Ni-Mo2C＞Fe-Mo2C，Co-Mo2The catalyst performance is optimal.
Co-Mo prepared in example 12The taffy polarization curves of Pt prepared in C and comparative example 1 are shown in fig. 8, and the electrochemical impedance spectrum is shown in fig. 9, in which the inset is an equivalent fitted circuit diagram. Exchange current density J0And the charge transfer resistance R obtained in the electrochemical impedance spectroscopyctIn inverse proportion, the specific formula is Rct＝RT/nFJ0Where R is the gas constant, T is the test temperature (25 ℃), n is the electron transfer number, and F is the Faraday constant. As is clear from FIGS. 8 to 9, the charge transfer resistance of the transparent counter electrode prepared in example 1 was 10.05. omega. cm2In comparative example 1, the charge transfer resistance of Pt was 5.20. omega. cm2Explanation, Pt electrode phase prepared in comparison with comparative example 1In contrast, the transparent counter electrode prepared in example 1 had comparable electrocatalytic activity.
(3) Photoelectric conversion efficiency test
Dye-sensitized solar cell: the photo-anode is TiO loaded with N719 dye2Porous membrane with electrolyte I-/I3 -Oxidation reduction electrolyte and counter electrode were Co-Mo prepared in example 1, respectively2C and Pt prepared in comparative example 1.
For solar cells, the short-circuit current JscOpen circuit voltage VocFill factor FF and conversion efficiency η are the 4 most important parameters, a standard simulated sunlight (100mW cm)-2AM1.5G) is shown in FIG. 10 and Table 2, wherein the front side irradiation is named Co-Mo2C-F, Pt-F, back side illumination named Co-Mo2C-R、Pt-R。
TABLE 2 voltammetric curve of dye-sensitized solar cell
Figure BDA0002589173260000121
As is clear from FIG. 10 and Table 2, Co-Mo obtained in example 12C is short-circuit current density J of battery with counter electrodescIs 13.0mA · cm-2Open circuit voltage VocThe contrast ratio of the back irradiation to the front irradiation efficiency is 76%, compared with a Pt electrode (59%), the contrast ratio is obviously improved, the light absorption of the counter electrode with high transmittance during the back irradiation can be obviously reduced, the light utilization rate is further improved, and reference is provided for the development of novel dye-sensitized solar cells.
Example 8
The dye-sensitized solar cell comprises the following components: the photo-anode is TiO loaded with N719 dye2Membrane, electrolyte is I-/I3 -Redox electrolyte, Co-Mo prepared in example 12And C is a counter electrode.
Ultrasonic cleaning FTO substrate with thickness of 2.2mm in liquid detergent, acetone and ethanol respectively15min, taking out, drying, treating with ultraviolet ozone for 15min, and placing in 40mM TiCl4Soaking in the aqueous solution, keeping the temperature in a 70 ℃ oven for 30min, taking out and drying to obtain pretreated FTO; making TiO by screen printing2The slurry (purchased from Yingkou Aopingte New energy science and technology Co., Ltd., average particle size of 30nm) was scraped on the surface of the pretreated FTO to obtain TiO 11 μm thick2A film; subjecting the TiO to a reaction2The membrane was placed in 40mM TiCl4Soaking in water solution, keeping in a 70 ℃ oven for 20min, taking out, drying, placing in a resistance furnace, annealing at 500 ℃ for 30min, taking out when the temperature of the resistance furnace is reduced to 100 ℃, soaking in 300 mu M N719 dye for 24h, taking out, drying, and obtaining the photoanode.
Electrolyte composition of redox electrolyte: 0.6mol/L of 1, 3-dimethyl imidazole iodonium salt, 0.1mol/L of guanidine thiocyanate, 0.03mol/L of iodine simple substance, 0.05mol/L of lithium iodide and 0.5mol/L of 4-tert-butyl pyridine, wherein the solvents are acetonitrile and valeronitrile with the volume ratio of 85: 15.
To illustrate the relationship between short circuit current, open circuit voltage, fill factor and photoelectric conversion efficiency, the current was tested as a function of voltage, as shown in fig. 11, where the test conditions of the current-voltage curve are: measured by a Keithley 2400 source meter, the light intensity is 100mW/cm under standard sunlight2Irradiating the dye-sensitized solar cell with an illumination area of 0.1256cm2Applying a voltage of 0-0.8V.
Short-circuit current Jsc: the current density when the circuit state is short-circuited in light irradiation (the current density is generally used because the magnitude of the battery current is related to the area) can be obtained from the ordinate intercept when V is 0 in fig. 11.
Open circuit voltage Voc: the voltage of the dye-sensitized solar cell when the circuit is open during illumination (the external circuit resistance is sufficiently large) is represented by J in FIG. 11scThe abscissa intercept can be found at 0.
Fill factor FF, the calculation formula is:
Figure BDA0002589173260000131
the photoelectric conversion efficiency is a standard for judging the quality of the DSCs battery, is a ratio of the maximum output power to the incident power of the device under the illumination condition, and a calculation formula of the photoelectric conversion efficiency η is as follows:
Figure BDA0002589173260000132
fill factor FF of dye-sensitized solar cell is 0.78, Jsc＝15.97mA/cm2，Voc＝0.67，η＝8.37％。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A non-platinum-based transparent electrode material, which comprises an FTO substrate, a molybdenum-based transparent conductive carrier film positioned on the surface of the FTO substrate and a non-platinum transition metal positioned on the surface of the molybdenum-based transparent conductive carrier film; the particle size of the non-platinum transition metal is less than or equal to 5 nm; the thickness of the molybdenum-based transparent conductive carrier film is 5-30 nm.
2. The non-platinum based transparent electrode material of claim 1, wherein the non-platinum transition metal comprises cobalt, nickel, copper, or iron.
3. The non-platinum transparent electrode material as claimed in claim 1, wherein the material of the molybdenum-based transparent conductive support film comprises Mo2C or MoO3。
4. A method for preparing the non-platinum-based transparent electrode material according to any one of claims 1 to 3, comprising the steps of:
performing magnetron sputtering on the surface of the FTO substrate by taking a molybdenum-based conductive carrier as a target to obtain an FTO-molybdenum-based transparent conductive carrier film;
and placing the FTO-molybdenum-based transparent conductive carrier membrane into a non-platinum transition metal salt solution for dipping, and calcining under a protective atmosphere to obtain the non-platinum-based transparent electrode material.
5. The method of claim 4, wherein the operating parameters of the magnetron sputtering include: the reaction gas is argon, the pressure is 0.6-0.8 Pa, the power is 60-80W, the temperature is 20-300 ℃, and the time is 0.5-3 min.
6. The method according to claim 4, wherein the non-platinum transition metal salt in the non-platinum transition metal salt solution comprises a cobalt salt, a nickel salt, a copper salt, or an iron salt;
the concentration of the non-platinum transition metal salt solution is 5-20 mmol/L.
7. The preparation method according to claim 4 or 6, wherein the impregnation is carried out at room temperature for 3-5 h.
8. The preparation method according to claim 4, wherein the calcination temperature is 400 to 500 ℃, the temperature rise rate for raising the temperature to the calcination temperature is 400 to 450 ℃/min, and the holding time is 10 to 15 min.
9. Use of the non-platinum-based transparent electrode material according to any one of claims 1 to 3 or the non-platinum-based transparent electrode material prepared by the preparation method according to any one of claims 4 to 8 in a dye-sensitized solar cell.
CN202010690481.9A 2020-07-17 2020-07-17 Non-platinum-based transparent electrode material and preparation method and application thereof Active CN111681879B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010690481.9A CN111681879B (en) 2020-07-17 2020-07-17 Non-platinum-based transparent electrode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010690481.9A CN111681879B (en) 2020-07-17 2020-07-17 Non-platinum-based transparent electrode material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111681879A true CN111681879A (en) 2020-09-18
CN111681879B CN111681879B (en) 2021-12-07

Family

ID=72457767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010690481.9A Active CN111681879B (en) 2020-07-17 2020-07-17 Non-platinum-based transparent electrode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111681879B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740237A (en) * 2008-11-21 2010-06-16 中国科学院物理研究所 Method for preparing carbon nanotube counter electrode for dye-sensitized solar cell
CN105977035A (en) * 2016-07-27 2016-09-28 杨炳 Dye-sensitized solar cell of novel electrode structure
CN110491675A (en) * 2019-09-12 2019-11-22 东北师范大学 A kind of transparent counter electrode and the preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740237A (en) * 2008-11-21 2010-06-16 中国科学院物理研究所 Method for preparing carbon nanotube counter electrode for dye-sensitized solar cell
CN105977035A (en) * 2016-07-27 2016-09-28 杨炳 Dye-sensitized solar cell of novel electrode structure
CN110491675A (en) * 2019-09-12 2019-11-22 东北师范大学 A kind of transparent counter electrode and the preparation method and application thereof

Also Published As

Publication number Publication date
CN111681879B (en) 2021-12-07

Similar Documents

Publication Publication Date Title
Chen et al. Fabrication of high performance Pt counter electrodes on conductive plastic substrate for flexible dye-sensitized solar cells
Khoo et al. One‐Step Hydrothermal Tailoring of NiCo2S4 Nanostructures on Conducting Oxide Substrates as an Efficient Counter Electrode in Dye‐Sensitized Solar Cells
Kim et al. Improved performance of quantum dot-sensitized solar cells adopting a highly efficient cobalt sulfide/nickel sulfide composite thin film counter electrode
Li et al. High-performance and low platinum loading Pt/Carbon black counter electrode for dye-sensitized solar cells
Li et al. Improvement of performance of dye-sensitized solar cells based on electrodeposited-platinum counter electrode
Sedghi et al. Influence of TiO2 electrode properties on performance of dye-sensitized solar cells
Kim et al. Facile chemical bath deposition of CuS nano peas like structure as a high efficient counter electrode for quantum-dot sensitized solar cells
Nemoto et al. All-plastic dye-sensitized solar cell using a polysaccharide film containing excess redox electrolyte solution
Kim et al. Nickel doped cobalt sulfide as a high performance counter electrode for dye-sensitized solar cells
Kim et al. Cost-effective and morphology controllable PVP based highly efficient CuS counter electrodes for high-efficiency quantum dot-sensitized solar cells
Kumar et al. Synthesis and characterization of carbon based counter electrode for dye sensitized solar cells (DSSCs) using organic precursor 2-2′ Bipyridine (Bpy) as a carbon material
Peiris et al. Stacked rGO–TiO2 photoanode via electrophoretic deposition for highly efficient dye-sensitized solar cells
CN103021668A (en) Semiconductor nanocrystalline sensitized solar cell and preparation method thereof
De Rossi et al. Blending CoS and Pt for amelioration of electrodeposited transparent counterelectrodes and the efficiency of back-illuminated dye solar cells
Congiu et al. Single precursor route to efficient cobalt sulphide counter electrodes for dye sensitized solar cells
CN104952626B (en) It is a kind of nanocrystalline to electrode and preparation method thereof
JP2013539168A (en) Counter electrode of dye-sensitized solar cell and method for producing the same
CN109637816B (en) Cu2S-SiW12/MoS2Composite counter electrode and preparation method thereof and quantum dot sensitized solar cell
Xiao et al. Low temperature fabrication of high performance and transparent Pt counter electrodes for use in flexible dye-sensitized solar cells
Lan et al. Improvement of Photovoltaic Performance of Dye-Sensitized Solar Cell by Post Heat Treatment of Polymer-Capped Nano-Platinum Counterelectrode
CN111755254B (en) Photoanode based on silver-indium-sulfur quantum dot sensitization, photoelectrochemical cell and preparation method
CN103714973B (en) A kind of Photoelectrochemistry Cu3snS4/ Cu2snSe3hybrid Photocathode and preparation method thereof
Kim et al. Long-term stability of conducting polymers in iodine/iodide electrolytes: Beyond conventional platinum catalysts
CN111681879B (en) Non-platinum-based transparent electrode material and preparation method and application thereof
Lee et al. Efficient and stable back-illuminated sub-module dye-sensitized solar cells by decorating SiO 2 porous layer with TiO 2 electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant