KR20170093414A - Dye-sensitized solar cell including polymer/graphene composite gel electrolyte and preparing methods thereof - Google Patents
Dye-sensitized solar cell including polymer/graphene composite gel electrolyte and preparing methods thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
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Abstract
Description
The present invention relates to a dye-sensitized solar cell comprising a polymer / graphene composite gel electrolyte and a process for producing the dye-sensitized solar cell.
Dye-sensitized solar cells (DSCs) are promising photovoltaic devices due to their high photoelectric conversion efficiency (?), Low manufacturing cost, and potential for the fabrication of transparent devices. A typical dye-sensitized solar cell uses a liquid electrolyte (LE) solution as a hole-transport medium, which causes leakage and evaporation of the liquid solvent, thereby reducing the device efficiency over time. To overcome these problems, many studies have suggested replacing the liquid electrolyte with a solid or pseudo-solid electrolyte comprising a polymer, a p-type semiconductor, a hole-transporting polymer, and a non-solvent ionic liquid. Of these materials, polymer-based solid electrolytes are competitive in cost and processing; The hole-transport materials have not yet been commercialized. Polymer-based electrolytes are well suited for the fabrication of flexible devices. Poly (vinylidene fluoride-co-hexafluoropropylene), poly (methyl methacrylate), poly (methyl methacrylate), and poly (vinylidene fluoride-co-hexafluoropropylene) Various polymers were applied in the dye-sensitized solar cell, including poly (acrylonitrile-co-vinyl acetate), polyacrylonitrile and polyacrylonitrile. In polymer gel electrolytes (PEG), the polymer immobilizes solvent molecules with van der Waals forces, thereby dramatically reducing the amount of solvent available. Polymer gel electrolytes are SiO 2, TiO 2, and a variety of carbon nanomaterial is often combined with [for example, carbon nanotubes (CNT), graphene], nanoparticle filler containing; The nanoparticle filler complements the low diffusion of electrolyte ions in the polymer matrix and the low conductivity of the polymer gel electrolyte film. Specifically, carbon nanomaterials tend to improve conductivity and ion dissociation due to their high adsorption to lithium ions; For example, PEO / CNT composites showed 3 times higher ion diffusivity compared to PEO, and PMMA / CNT composites showed 3 times higher conductivity than bare PMMA.
However, the application of polymer gel electrolytes to dye-sensitized solar cells poses a practical problem. In the production of a typical dye-sensitized solar cell, the electrolyte is injected into the gap between the photoelectrode and the counter electrode at the final stage of the cell assembly; These gaps are typically tens of micrometers wide. Therefore, the injection of the high viscosity polymer gel electrolyte requires a high pressure which may affect the cell. It is also challenging to inject the polymer gel electrolyte completely between mesoscale pores of a conventional TiO 2 light-absorbing electrode film. In this case, most studies on polymer gel electrolytes in dye-sensitized solar cells have used very low wt% polymers to form diluted polymer gel electrolytes. In order to facilitate the injection of the polymer gel electrolyte, attempts have been made to control the gelation rate of the polymer-dissolved liquid electrolyte. Recently, a new strategy based on in situ gelation with a polymer / particle-deposited substrate has been proposed; The polymer gel electrolyte was prepared by depositing polymer particles on the electrode, assembling the cell, and injecting an electrolyte solution to dissolve the polymer particles. Since the polymer gel electrolyte was prepared after the cell was assembled, the problems generally associated with injection and filling of excellently prepared polymer gel electrolyte were eliminated. However, previous approaches have been demonstrated using only polystyrene particles, which have relatively low compatibility with only acetonitrile-based electrolyte solvents; Therefore, it is still challenging to use highly compatible polymeric particles in the proposed in situ approach.
Korean Patent Laid-Open No. 10-2013-0145664 relates to a composite polymer electrolyte for a lithium secondary battery and a method for producing the same, and discloses a solid polymer electrolyte using a branched polymer and graphene oxide.
The present invention provides a dye-sensitized solar cell comprising a polymer / graphene composite gel electrolyte and a method of manufacturing the dye-sensitized solar cell.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a polymer particle layer on a counter electrode; Coating graphene flakes on the polymer particle layer; And an electrolyte solution is injected into a gap between the counter electrode and the photo electrode to form a polymer matrix by the in-situ gelation of the polymer particle layer by a solvent contained in the electrolyte solution, Dispersed in a matrix to form a polymer / graphene composite gel electrolyte.
The second aspect of the present invention is a dye-sensitized solar cell comprising a polymer / graphene composite gel electrolyte containing graphene flakes dispersed in a polymer matrix, wherein the polymer / graphene composite gel electrolyte is a dye- The polymer particle layer previously coated on the counter electrode is in-situ gelled by the solvent contained in the electrolyte solution injected into the gap between the counter electrode and the photo electrode to form the polymer matrix, Wherein the graphene flakes previously coated on the particle layer are dispersed in the polymer matrix.
According to an embodiment of the present invention, polymer particles having excellent compatibility with an electrolyte solution, particularly a solvent contained in an electrolyte solution, and graphene flakes having excellent conductivity are coated on a counter electrode, A high concentration polymer / graphene composite gel electrolyte in which the polymer particle layer is gelated to form a polymer matrix and the graphene flake is dispersed on the gelated polymer matrix by injecting an electrolyte into a gap, The dye-sensitized solar cell can be manufactured.
In the polymer / graphene composite gel electrolyte of the dye-sensitized solar cell according to an embodiment of the present invention, the ion diffusivity and the conductivity are increased due to the addition of graphene, so that the photoelectric conversion efficiency comparable to that of the conventional liquid electrolyte can be secured , And thus can be applied to energy devices such as lithium batteries and capacitors that require a stable electrolyte system. In addition, the dye-sensitized solar cell according to one embodiment of the present invention is characterized in that when the polymer gel electrolyte is injected in the process of manufacturing the dye-sensitized solar cell, the electrolyte is incompletely injected into the electrode pores due to the high viscosity of the polymer gel electrolyte. And the efficiency can be reduced.
1 is a schematic diagram illustrating the in situ formation of PMMA and PMMA / graphene composite gel electrolyte in one embodiment of the present invention.
2 (a) and 2 (b) are surface SEM images of the PMMA spherical particle layer (a) and the PMMA / graphene composite layer (b), in one embodiment of the present invention.
3 (a) and 3 (b) are graphs showing Raman spectra (a) of PMMA and PMMA / graphene films and XPS C 1s spectrum (b) of graphene powder in one embodiment of the present invention .
4 is a schematic diagram of a dye-sensitized solar cell (DSC) fabricated using LE (liquid electrolyte), PMMA i-PGE (in situ-polymer gel electrolyte), and PMMA / ) ≪ / RTI >
5 is a Nyquist plot for a dye-sensitized solar cell fabricated using LE, PMMA i-PGE, and PMMA / graphene i-PGE in one embodiment of the present invention.
Figures 6 (a) - (d) show, in an embodiment of the invention, that during the heat treatment at 60 占 폚, the dye-sensitized solar cell fabricated using LE, PMMA i-PGE, and PMMA / Lt; RTI ID = 0.0 > normalized < / RTI > photoelectric parameters for the cell.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.
Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.
Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.
Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.
Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.
Throughout this specification, the description of "A and / or B" means "A or B, or A and B".
Throughout this specification, the term "graphene " means that a plurality of carbon atoms are covalently linked to one another to form a polycyclic aromatic molecule, wherein the carbon atoms linked by the covalent bond are the same as the basic repeating
Throughout the specification, the term "graphene oxide" is also referred to as graphene oxide and may be abbreviated as "GO ". But not limited to, a structure in which a functional group containing oxygen such as a carboxyl group, a hydroxyl group, or an epoxy group is bonded on a single layer graphene.
Throughout this specification, the term "reduced graphene oxide" or "reduced graphene oxide" refers to a graphene oxide that has undergone a reduction process to reduce its oxygen content and can be abbreviated as "rGO" But is not limited thereto.
Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.
According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a polymer particle layer on a counter electrode; Coating graphene flakes on the polymer particle layer; And an electrolyte solution is injected into a gap between the counter electrode and the photo electrode to form a polymer matrix by the in-situ gelation of the polymer particle layer by a solvent contained in the electrolyte solution, Dispersed in a matrix to form a polymer / graphene composite gel electrolyte.
In one embodiment of the present invention, the polymer particle layer may be formed by in-situ gelation using a solvent contained in the electrolyte solution to form a polymer matrix, but the present invention is not limited thereto. FIG. 1 is a schematic view illustrating a process of manufacturing a dye-sensitized solar cell including a polymer / graphene composite gel electrolyte according to an embodiment of the present invention.
As shown in FIG. 1, the dye-sensitized solar cell is formed of a counter electrode, a polymer particle layer formed on the counter electrode, a graphene flake coated on the polymer particle layer, and a photo electrode. As in the first process of FIG. 1, the polymer particle layer is formed by coating the polymer spherical particle on the counter electrode. The graphene flake is coated on the formed polymer particle layer (step A), and the polymer particle and the counter electrode coated with graphene flake are combined with the photo electrode to form a gap (step B). When the dye-sensitized solar cell is assembled as in step B, an electrolyte is injected into a gap between the counter electrode and the photo electrode to gel the polymer particles to form a polymer matrix, and the graphene The flakes are dispersed to form a transparent polymer / graphene composite gel electrolyte by in situ gelation (step C).
In one embodiment of the present invention, the polymer may be a polymer used in a conventional gel electrolyte, and particularly, has good affinity or compatibility with a solvent or a mixed solution of an electrolyte used in a dye-sensitized solar cell, Any polymer that is easy to form into particles can be used without particular limitation.
In one embodiment of the present invention, the polymer may include a conductive polymer and / or a nonconductive polymer. For example, the polymer may include polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF) , Polyethylene oxide (PEO), polyurethane (PU), polyacrylonitrile, polyacrylamide, polyvinyl acetate, polyvinyl pyrrolidinone, poly But are not limited to, those selected from the group consisting of polytetraethylene glycol diacrylate, polystyrene (PS), and combinations thereof.
In one embodiment of the present invention, the method of forming the polymer particle layer is not particularly limited and may be, for example, coating on the counter electrode by dip-coating or spin coating, but is not limited thereto .
In one embodiment of the present invention, the graphene flake coating method is not particularly limited and may be, for example, coating the polymer particle layer by an electrospray method, but is not limited thereto .
In one embodiment of the present invention, the solvent contained in the electrolytic solution may include, but is not limited to, an organic solvent. For example, the organic solvent may be used without limitation as long as it can cause in situ gelation through gelation of the polymer particles and dispersion of graphene flakes. The organic solvent may include, but not limited to, a nitrile-based solvent have.
In one embodiment, the nitrile-based solvent is selected from the group consisting of acetonitrile, 3-methoxypropionitrile, propionitrile, butyronitrile, t-butyl cyanide, But are not limited to, nitrile, nitrile, nitrile, nitrile, nitrile, nitrile, nitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentanecarbonitrile, cyclohexanecarbonitrile, 2- fluorobenzonitrile, Chlorobenzonitrile, dichlorobenzonitrile, trichlorobenzonitrile, 2-chloro-4-fluorobezonitrile, 4-chloro-2-fluoro But are not limited to those selected from the group consisting of benzenesulfonyl chloride, benzenitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, 4-fluorophenylacetonitrile, But may not be limited thereto.
In one embodiment of the invention, the organic solvent may include, but is not limited to, acetonitrile, valeronitrile, or mixtures thereof.
In one embodiment of the present invention, the organic solvent may well dissolve ions favorable for electron transfer. For example, the organic solvent may well disperse the polymer (particle) contained in the electrode of the dye- But it may be, but not limited to.
In one embodiment of the present invention, the solubility of the polymer may vary depending on the type of the organic solvent and / or the compatibility with the organic solvent, but the present invention is not limited thereto. For example, when the polymer particles are polymethylmethacrylate (PMMA) and the organic solvent is a mixture of acetonitrile and valeronitrile, as the content of the valeronitrile in the organic solvent increases, Dispersion and gelation may occur quickly, but may not be limited thereto.
In one embodiment of the present invention, the minimum polymer content of gelation of the polymer gel electrolyte may vary depending on the type of the organic solvent, but may not be limited thereto.
In one embodiment of the present invention, the content of the polymer matrix may be about 20 parts by weight or less based on 100 parts by weight of the polymer / graphene composite gel electrolyte, but may not be limited thereto. For example, the content of the polymer matrix is about 20 parts by weight or less, about 1 to about 20 parts by weight, about 1 to about 15 parts by weight, about 1 to about 10 parts by weight based on 100 parts by weight of the polymer / From about 5 to about 20 parts by weight, from about 5 to about 15 parts by weight, from about 5 to about 10 parts by weight, from about 10 to about 20 parts by weight, from about 10 to about 15 parts by weight, or from about 15 to about 20 parts by weight But may not be limited thereto.
In one embodiment of the present invention, the content of the graphene flake may be about 10 parts by weight or less based on 100 parts by weight of the polymer / graphene composite gel electrolyte, but may not be limited thereto. For example, the content of graphene flake may be about 10 parts by weight or less, about 0.1 to about 10 parts by weight, about 0.1 to about 8 parts by weight, about 0.1 to about 8 parts by weight based on 100 parts by weight of the polymer / About 0.1 to about 2 parts by weight, about 0.1 to about 1 part by weight, about 1 to about 10 parts by weight, about 1 to about 8 parts by weight, about 1 to about 6 parts by weight About 2 to about 6 parts by weight, about 2 to about 4 parts by weight, about 1 to about 4 parts by weight, about 1 to about 2 parts by weight, about 2 to about 10 parts by weight, about 2 to about 8 parts by weight, About 4 to about 10 parts by weight, about 4 to 8 parts by weight, about 4 to about 6 parts by weight, or about 8 to about 10 parts by weight.
The second aspect of the present invention is a dye-sensitized solar cell comprising a polymer / graphene composite gel electrolyte containing graphene flakes dispersed in a polymer matrix, wherein the polymer / graphene composite gel electrolyte is a dye- The polymer particle layer previously coated on the counter electrode is in-situ gelled by the solvent contained in the electrolyte solution injected into the gap between the counter electrode and the photo electrode to form the polymer matrix, Wherein the graphene flakes previously coated on the particle layer are dispersed in the polymer matrix.
In one embodiment of the present invention, the dye-sensitized solar cell may be manufactured by a method according to the first aspect of the present invention, but the present invention is not limited thereto. Although the description of the dye-sensitized solar cell according to the second aspect of the present invention is omitted from the description of the first aspect of the present invention, the description of the first aspect of the present invention is not limited to the second The same can be applied to the side.
In one embodiment of the present invention, the polymer particle layer may be formed by gelation with a solvent contained in the electrolyte solution to form a polymer matrix, but the present invention is not limited thereto.
In one embodiment of the present invention, the polymer may be a polymer used in a conventional gel electrolyte, and particularly, has good affinity or compatibility with a solvent or a mixed solution of an electrolyte used in a dye-sensitized solar cell, Any polymer that is easy to form into particles can be used without particular limitation.
In one embodiment of the present invention, the polymer may include a conductive polymer and / or a nonconductive polymer. For example, the polymer may include polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF) , Polyethylene oxide (PEO), polyurethane (PU), polyacrylonitrile, polyacrylamide, polyvinyl acetate, polyvinyl pyrrolidinone, poly But are not limited to, those selected from the group consisting of polytetraethylene glycol diacrylate, polystyrene (PS), and combinations thereof.
In one embodiment of the present invention, the solvent contained in the electrolytic solution may include, but is not limited to, an organic solvent. For example, the organic solvent may be used without limitation as long as it can cause in situ gelation through gelation of the polymer particles and dispersion of graphene flakes. The organic solvent may include, but not limited to, a nitrile-based solvent have.
In one embodiment, the nitrile-based solvent is selected from the group consisting of acetonitrile, 3-methoxypropionitrile, propionitrile, butyronitrile, t-butyl cyanide, But are not limited to, nitrile, nitrile, nitrile, nitrile, nitrile, nitrile, nitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentanecarbonitrile, cyclohexanecarbonitrile, 2- fluorobenzonitrile, Chlorobenzonitrile, dichlorobenzonitrile, trichlorobenzonitrile, 2-chloro-4-fluorobezonitrile, 4-chloro-2-fluoro But are not limited to those selected from the group consisting of benzenesulfonyl chloride, benzenitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, 4-fluorophenylacetonitrile, But may not be limited thereto.
In one embodiment of the invention, the organic solvent may include, but is not limited to, acetonitrile, valeronitrile, or mixtures thereof.
In one embodiment of the present invention, the organic solvent is capable of dissolving ions favorable for electron transfer. For example, the organic solvent may disperse and gel the polymer particles contained in the electrode of the dye- But it is not so limited.
In one embodiment of the present invention, the solubility of the polymer may vary depending on the type of the organic solvent and / or the compatibility with the organic solvent, but the present invention is not limited thereto. For example, when the polymer particles are polymethylmethacrylate (PMMA) and the organic solvent is a mixture of acetonitrile and valeronitrile, as the content of the valeronitrile in the organic solvent increases, Dispersion and gelation may occur quickly, but may not be limited thereto.
In one embodiment of the present invention, the minimum polymer content of gelation of the polymer gel electrolyte may vary depending on the type of the organic solvent, but may not be limited thereto.
In one embodiment of the present invention, the dye-sensitized solar cell is formed by incompletely injecting into the pores of the electrode due to the high viscosity of the polymer gel electrolyte, which occurs upon injecting the polymer gel electrolyte in the manufacturing process of the conventional dye- However, the present invention is not limited thereto.
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are given to aid understanding of the present invention, and the present invention is not limited to the following examples.
[ Example ]
Polymethyl methacrylate (PMMA) particles and Grapina Preparation of composite layer
PMMA sphere particles were synthesized by emulsion polymerization. The polymerization was carried out for 24 hours at 70 DEG C with 14 wt% MMA monomer, 0.3 wt% (relative to the weight of the monomer) 2,2'-azobis (2-methylpropiopyranidine) -methylpropionamidine) initiator, and deionized water. The particles were purified by several sedimentation, centrifugation, and dispersion in water. The PMMA spheres were coated on a Pt-coated transparent electrode which is a counter electrode by a dip-coating method. The Pt-coated transparent electrode was prepared by coating a 0.7 mM H 2 PtCl 6 solution in anhydrous ethanol on an FTO substrate. Graphene flake powder (Angstron Materials) having an oxygen content of about 1.5% was dispersed in isopropyl alcohol and made up to 0.3 wt% in the graphene dispersion solution. The graphene-dispersed solution was electrosprayed onto the PMMA spherical particle layer. The applied voltage was 2.0 kV at the spray nozzle using an acceleration of 24 G, and the feed flow rate was about 30 μm min -1 .
Assembly of dye-sensitized solar cell
Conventional nanocrystalline TiO 2 The photoelectrode film was prepared by doctor blade coating. The TiO 2 The area of the nanoparticle (NP) film was adjusted by scraping to be about 8-10 mm 2 . The TiO 2 film was soaked overnight in 0.5 mM D205 in acetonitrile and sensitized to D205 dye (Mitsubishi Paper Mills). The Pt counter electrode was prepared by coating a solution of 0.7 mM H 2 PtCl 6 in anhydrous ethanol on the FTO substrate. The TiO 2 NP-coated FTO substrate and the counter electrode were assembled and the gap between the two electrodes was fixed using a 60 μm-thick polymeric film (Surlyn, DuPont). Finally, the electrolyte was injected between the gaps; Electrolytic solution of acetonitrile (Aldrich) and valeronitrile (valeronitrile) a solution containing (85:15 v / v) 0.05 M LiI (Sigma-Aldrich), 0.1 M guanidine thiocyanate (guanidine thiocyanate) (Wako), 0.03 MI 2 (Yakuri), 0.5 M 4- tert - butyl-pyrimidin nidin (Aldrich), and 0.7 M 1- butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide) (BMII) ( Sigma-Aldrich).
Character analysis
The diffusivity of the polymer gel electrolyte was measured by cyclic voltammetry (Versatat, Ametek), and the conductivity was measured by impedance spectroscopy (Versatat, Ametek). For this measurement, a cell having two Pt-coated FTO electrodes containing the polymer gel electrolyte between the two electrodes was prepared. SEM images were obtained using a field-emission scanning electron microscope (Hitachi S-4700). Raman spectra were recorded at 487.55 nm excitation wavelength using micro-Raman spectroscopy (Tokyo Instruments, Nanofinder). The JV characteristics of the dye-sensitized solar cell were measured using a source meter (Keithley Instruments) under simulated sunlight provided by a solar simulator (1000 W Xe lamp with AM 1.5 G filter). The light intensity was adjusted to 100 mWcm -2 using a Si reference cell (BS-520, Bunko-Keiki). The electrochemical impedance of the dye-sensitized solar cell was analyzed by impedance spectroscopy using an impedance analyzer (Versastat, AMETEK). The measurements were performed in the frequency range of 10 5 to 0.1 Hz with 10 mV perturbation amplitude under dark or 1-sun illumination conditions. The data was adjusted by an equivalent circuit provided by Z-View software (Scribner Associates, Inc.).
Describing this embodiment with reference to Figure 1, the preparation of a PMMA / graphene in situ-dye-sensitized solar cell (i-PGE) is described. The PMMA spherical particles were deposited on a Pt-coated FTO counter electrode and the graphene flakes were deposited on the PMMA sphere layer (step A). The PMMA / graphene-coated FTO substrate was interposed between the TiO 2 light electrodes. The electrolyte was injected into the gap between the photoelectrode and the PMMA / graphene counter electrode (step B). As shown in Figure 1, the cell was transparent, which was observed to be caused by gelation of the PMMA into the electrolyte and by the above dispersion of graphene flakes (step C). The thickness of the PMMA layer was adjusted to 2 [mu] m, which formed about 12 wt% PMMA gel solution. Complete gelation of the PMMA particle-containing electrolyte was confirmed by increasing the volume of the electrolyte solution. The optimum wt% of graphene was determined by a continuous comparison of the graphene content to the efficiency of the dye-sensitized solar cell using the i-PGE composite; The 0.3 wt% graphene-based i-PGE dye-sensitized solar cell showed the highest efficiency compared to 0.1 wt% and 0.6 wt% graphene samples.
The surface SEM image of the PMMA particle layer was characterized by 250 nm-diameter PMMA spheres (Fig. 2 (a)). The thickness of the PMMA layer was about 1.8 占 퐉 as shown in the inset of FIG. 2 (a). The PMMA / graphene composite layer exhibited graphene flake dispersion over an area of about 5 x 5 m on the PMMA surface (Fig. 2 (b)). The digital image of the composite layer was shown on a gray-scale basis based on the presence of graphene in the inset of FIG. 2 (b).
The PMMA and PMMA / graphene films were also characterized using Raman spectra. Strong peaks at 1460 cm 1 , 1740 cm 1 , and 2950 cm 1 are due to CH bending, C = C / C-COO stretching of alpha -CH 3 in the PMMA molecules as shown in FIG. ), and in agreement with each ester -CH 3 stretching. In the PMMA / graphene composite film, 1360 cm < And additional strong peaks at 1590 cm < 1 > These peaks are characteristic of carbon; The former relates to in-plane graphite disorder or edge defect (i. E. D band), while the latter relates to in-plane sp 2 Carbon vibration (i.e., G band). The intensity ratio (I D / I G ) of the D to G bands was about 1.3. The graphene flakes were expected to possess the properties of reduced graphene oxide, since the above rates of reduced graphene oxide obtained by chemical approaches are often above 1.0. The 2D band around 2700 cm <" 1 > was also observed. The intensity of the 2D band was relatively weak compared to that of the G band, and the 2D band exhibited smaller splitting. This result can mean dispersion of multi-layer graphene.
The graphene flakes were also characterized using XPS. The C 1s peak in the XPS spectrum was explained by four different peaks at 284.6 eV for CC / C = C bond, 285.9 eV for CO, 287.1 eV for C = O, and 288.6 eV for OC = 0 . Taking into account the relative content of these functional groups, the graphene flake powder possesses a high proportion of CC / C = C bonds as compared to other oxygenated groups, Prove existence.
The ion diffusion coefficients in the original PMMA and PMMA / graphene i-PGE were measured using saturation current conditions in which the ion diffusion is limited in the electrolyte. The diffusion coefficient of the liquid electrolyte (LE) was also measured for comparison. Since I - is dominant in the liquid electrolyte, the limiting current was determined by I 3 - ions. First law of Fick against ion diffusion (Fick's First Law), J = 2nFCD / l has been applied, where J is the saturation current, n is the number of transmission E (that is, 3-reduction of I during the reaction; Therefore, , n = 2), F is the Faraday constant, C is the diffusivity of the bulk density, D is the 3- I ion of the 3- I ion, I is the thickness of the electrolyte layer. Table 1 shows the ion-diffusivity and ionic conductivity of the LE (liquid electrolyte), PMMA i-PGE (PMMA-based in situ-polymer gel electrolyte) and PMMA / graphene i-PGE, The diffusion coefficient of -PGE was 1/3 of the diffusion coefficient of LE as shown in Table 1 below. The use of PMMA increased the viscosity of the electrolyte and thus limited ion mobility. The addition of graphene filler increased the diffusion coefficient by about 20% compared to the PMMA i-PGE, which is also shown in Table 1. It has been reported that the cabronaceous filler improves the dissociation of LiI and maintains a high concentration of electrolyte ions; This effect has resulted in an increase in the apparent diffusion coefficient.
The conductivities of the LE, original PMMA i-PGE, and PMMA / graphene i-PGE films were calculated using the equation σ = L / R b A, where σ is the conductivity; L and A are respectively and the film thickness and area, and R b is the bulk resistance measured by the impedance plot. The PMMA i-PGE film was found to have a lower conductivity than the LE (Table 1). The measured conductivity of the PMMA i-PGE was slightly lower than that of the conventional PMMA PGE with 1-3 mScm -1 ; This finding may be the result of higher concentrations of PMMA (10 wt%) in the i-PGE, compared to those used in other studies, which is typically less than 5 wt%. The PMMA / graphene PMMA i-PGE exhibited a higher conductivity than the PMMA i-PGE. The increase in the conductivity by the addition of carbon material in the polymer film, such as carbon nanotubes and graphene, has been well studied; Carbon fillers are known to provide a conducting pathway.
The photoelectric performance of the dye-sensitized solar cell containing PMMA and PMMA / graphene i-PGE was evaluated by measuring photocurrent density and voltage (JV); The photoelectric properties of a dye-sensitized solar cell (LE DSC) comprising a liquid electrolyte were also compared. The short-circuit current density (J sc ), the open-circuit voltage (V oc ), and the fill factor (FF) were extracted from the JV profile shown in Figure 4 and Table 2 below; Table 2 shows the LE, PMMA i-PGE, and PMMA / graphene as shown the i-PGE the dye-sensitized photoelectric parameters of a solar cell and the photoelectric conversion efficiency system using, from this data, η is the relation η = J sc × V oc × FF / (100 mWcm - 2) was measured in accordance with. Compared with the dye-sensitized solar cell comprising a liquid electrolyte, the PMMA i-PGE dye-sensitized solar cell showed 7% lower J sc and 10% lower FF. This result is explained by the lower ion diffusion and conductivity caused by the presence of PMMA; The low diffusion of I 3 - ions induces electron recombination, reduces J sc , and a high series resistance reduces FF. Comparing the PMMA and PMMA / graphene i-PGE, the addition of graphene improves J sc and FF by 5% and 10%, respectively; This effect is also explained by the fact that graphene improves the ionic diffusion and conductivity of the PMMA-based i-PGE. Mineral fillers, such as SiO 2 and TiO 2 , have often been reported to reduce the conductivity of such materials. The? Of the PMMA-graphene i-PGE dye-sensitized solar cell is 8.49%, which is only 6% lower than that of the dye-sensitized solar cell (LE DSC) comprising the liquid electrolyte.
The electrochemical impedance spectra of LE, PMMA i-PGE, and PMMA / graphene i-PGE dye-sensitized solar cells were characterized. The three semicircles from the left indicate the resistance (e.g., 10 5 -30 Hz) associated with the electrochemical reaction at the Pt-electrolyte interface (R 1 ), the TiO 2 -dye-electrolyte interface (R (for example, 30 -1 Hz) and the ion-diffused resistor R 2 (for example, 1-10 -1 Hz), which are associated with the electrochemical reaction in the electrode ct . This resistance was obtained by fitting the plot to an equivalent circuit and is summarized in Table 3 below. Table 3 shows the interfacial resistance of the dye-sensitized solar cell containing LE, PMMA i-PGE, and PMMA / graphene i-PGE calculated by adjusting the equivalent circuit. In the electrolyte, Due to the presence of PMMA and graphene, R 1 was unaffected; R 2 not only increases with the addition of PMMA in the LE but also increases with incorporation of graphene, which corresponds to a change in diffusion coefficient. The R ct of the PMMA i-PGE dye-sensitized solar cell was found to be lower than that of the LE; This confirms that the lower diffusivity of the PMMA i-PGE adds the recombination rate, resulting in a lower J sc . Comparing PMMA with PMMA / graphene i-PGE, the addition of graphene reduces recombination and restores J sc .
Finally, long term stability was compared for dye-sensitized solar cell devices fabricated using LE, PMMA i-PGE, and PMMA / graphene i-PGE. The changes in the JV parameters (J sc , V oc , FF, and η) normalized by the initial values of the dye-sensitized solar cell prepared above during the aging time are shown in FIG. The dye-sensitized solar cell was exposed to thermal stress at 60 占 폚 in a dark state. The results show that the LE cell showed about 60%, which is a significant decrease in eta, while both of the two i-PGE dye-sensitized solar cells kept the eta to 90% of the initial value during the test period. The decrease in eta in the dye-sensitized solar cell comprising the liquid electrolyte was attributed to a decrease in J sc . Numerous studies have shown that leakage and evaporation of the electrolyte in LE cells cause a decrease in J sc ; Accordingly, the i-PGE effectively avoided the loss of the electrolyte solvent in order to maintain the performance similar to the conventional PGE system.
In situ formation of poly (methyl methacrylate) (PMMA) -based polymer-gel electrolyte (PGE) and graphene filler for use in quasi-solid dye-sensitized solar cells has been demonstrated. Wherein PMMA spherical particles and graphene flakes were deposited on the counter electrode, the dye-sensitized solar cell device was assembled, and finally the electrolyte was injected; The electrolyte solution dispersed and gelled the PMMA particles and dispersed the graphene to obtain a gelated electrolyte. By varying the amount of these materials used to form the desired coating, the PMMA and filler concentrations were simply controlled and a polymer gel electrolyte (PGE) concentration of at least 10 wt% was obtained. The PMMA i-PGE exhibited lower ion diffusivity and conductivity than the liquid electrolyte (LE), which resulted in a lower short-circuit current density and filling rate (FF) in the PMMA i-PGE dye-sensitized solar cell. Formation of the PMMA / graphene filler complex i-PGE improves both the diffusivity and the conductivity of the material. The dye-sensitized solar cell using PMMA / graphene i-PGE exhibited a photoelectric conversion efficiency (η) similar to that of a dye-sensitized solar cell including a liquid electrolyte. In the long-term stability test of the dye-sensitized solar cell under thermal immersion conditions, the dye-sensitized solar cell comprising the liquid electrolyte showed a remarkable drop of about 60% at?, Which may be the result of evaporation of the electrolyte solvent during the test , The PMMA / graphene i-PGE dye-sensitized solar cell maintained eta up to 90%. It is believed that the proposed in situ gelation method alleviates the problems caused by the injection of the polymer gel electrolyte in the conventional dye-sensitized solar cell manufacturing process while maintaining very stable device efficiency up to 90% of its initial value. Thus, this method can be applied to other energy devices, such as lithium batteries and capacitors, which require a stable electrolyte system.
It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
Claims (10)
Coating graphene flakes on the polymer particle layer; And
An electrolyte solution is injected into a gap between the counter electrode and the photoelectrode to form a polymer matrix by the in-situ gelation of the polymer particle layer by a solvent contained in the electrolyte solution, and the graphene flake is injected into the polymer matrix Thereby forming a polymer / graphene composite gel electrolyte
Wherein the dye-sensitized solar cell comprises a dye-sensitized solar cell.
Wherein the polymer has compatibility with a solvent contained in the electrolytic solution.
Wherein the polymer comprises a conductive polymer and / or a nonconductive polymer.
The polymer may be selected from the group consisting of polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polyurethane (PU), polyacrylonitrile, polyacrylimide, polyvinyl acetate, Wherein the polymer is selected from the group consisting of polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid,
Wherein the solvent contained in the electrolytic solution includes an organic solvent.
Wherein the content of the polymer matrix is 20 parts by weight or less based on 100 parts by weight of the polymer / graphene composite gel electrolyte.
Wherein the content of the graphene flake is 10 parts by weight or less based on 100 parts by weight of the polymer / graphene composite gel electrolyte.
Wherein the polymer particle layer is coated on the counter electrode by spin coating or dip coating.
Wherein the graphene flake is coated on the polymer particle layer by an electrospray method.
The polymer / graphene composite gel electrolyte may contain,
The polymer particle layer previously coated on the counter electrode is in-situ gelled by a solvent contained in an electrolyte solution injected into a gap between the counter electrode and the photo electrode included in the dye-sensitized solar cell, And the graphene flakes previously coated on the polymer particle layer are dispersed in the polymer matrix.
Dye - sensitized solar cell.
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| KR20190074753A (en) | 2017-12-20 | 2019-06-28 | 서강대학교산학협력단 | Dye-sensitized solar cell |
| KR20200031586A (en) | 2020-03-11 | 2020-03-24 | 서강대학교산학협력단 | Dye-sensitized solar cell |
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| KR20130132301A (en) * | 2012-05-25 | 2013-12-04 | 한국생산기술연구원 | Dye-sensitized solar cell having graphene coated carbon nano web |
| KR20130139450A (en) * | 2012-06-08 | 2013-12-23 | 성균관대학교산학협력단 | Gel-type polymer electrolyte for dye-sensitized solar cell and dye-sensitized solar cell comprising the same |
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| KR20130132301A (en) * | 2012-05-25 | 2013-12-04 | 한국생산기술연구원 | Dye-sensitized solar cell having graphene coated carbon nano web |
| KR20130139450A (en) * | 2012-06-08 | 2013-12-23 | 성균관대학교산학협력단 | Gel-type polymer electrolyte for dye-sensitized solar cell and dye-sensitized solar cell comprising the same |
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| KR20190074753A (en) | 2017-12-20 | 2019-06-28 | 서강대학교산학협력단 | Dye-sensitized solar cell |
| KR20200031586A (en) | 2020-03-11 | 2020-03-24 | 서강대학교산학협력단 | Dye-sensitized solar cell |
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