WO2014116026A1 - Graphene counter electrode for dye-sensitized solar cell, method for manufacturing same, and dye-sensitized solar cell comprising same - Google Patents

Graphene counter electrode for dye-sensitized solar cell, method for manufacturing same, and dye-sensitized solar cell comprising same Download PDF

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WO2014116026A1
WO2014116026A1 PCT/KR2014/000629 KR2014000629W WO2014116026A1 WO 2014116026 A1 WO2014116026 A1 WO 2014116026A1 KR 2014000629 W KR2014000629 W KR 2014000629W WO 2014116026 A1 WO2014116026 A1 WO 2014116026A1
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dye
counter electrode
solar cell
sensitized solar
graphene
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PCT/KR2014/000629
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French (fr)
Korean (ko)
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김환규
주명종
최인택
김상균
김재천
이재준
백종범
전인엽
최현정
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고려대학교 산학협력단
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a graphene counter electrode for a dye-sensitized solar cell, a manufacturing method thereof, and a dye-sensitized solar cell including the same.
  • dye-sensitized solar cells The principle of dye-sensitized solar cells is that dye molecules generate electron-hole pairs when sunlight (visible light) is absorbed by n-type nanoparticle semiconductor oxide electrodes with dye molecules chemically adsorbed on the surface, and the electrons are semiconductor It is injected into the conduction band of the oxide and is transferred to the transparent conductive film through the interface between nanoparticles to generate a current.
  • the hole receives electrons by the redox electrolyte and is reduced again, and the oxidized electrolyte receives electrons moved to the counter electrode. It is reduced again.
  • Pt platinum
  • WO98 / 050393 a counter electrode material used in dye-sensitized solar cells to date
  • Pt platinum
  • corrosiveness due to a reaction by an oxidation-reducing electrolyte is used. Due to the weak stability, in particular, because of the high price of Pt there was a problem that the economy is poor. Therefore, there is a need for the development of a new counter electrode material that can overcome this problem.
  • the present invention comprises the steps of: a) preparing a graphene compound doped with nitrogen elements by doping nitrogen to graphite; And b) surface treating the graphene compound prepared in step a) to an FTO transparent electrode by using an electrostatic spray deposition method. do.
  • the present invention also provides a graphene counter electrode for a dye-sensitized solar cell including a graphene compound doped with a nitrogen element.
  • the present invention provides a dye-sensitized solar cell including the graphene counter electrode.
  • Dye-sensitized solar cell comprising a graphene counter electrode of the present invention according to the solution of the above problem is very excellent in long-term stability, catalyst characteristics compared to the conventional solar cell using a Pt counter electrode.
  • Figure 1 (a) is a diagram schematically showing the production step of the graphene compound of Synthesis Example 1 of the present invention.
  • Figure 1 (b) is a diagram schematically showing the production step of the graphene compound of Synthesis Example 2 of the present invention.
  • FIG. 2 is a view schematically illustrating a step of manufacturing a counter electrode of the present invention.
  • Figure 3 (a) is a photograph showing the FTO surface state.
  • Figure 3 (b) is a photograph showing the state after the surface treatment of the graphene prepared in Synthesis Example 1 of the present invention to the FTO transparent electrode by the electrostatic radiation electrodeposition method.
  • Fig. 3 (c) is an enlarged photograph of the FTO surface state.
  • Figure 3 (d) is a photograph showing the state after surface treatment of the graphene prepared in Synthesis Example 2 of the present invention to the FTO transparent electrode by the electrostatic radiation electrodeposition method.
  • FIG. 8B is a graph measuring current-voltage curves of the counter electrodes manufactured in Examples 20 to 26 and Comparative Example 2 of the present invention.
  • Example 9 is a photograph of the enRP of the graphene compound of the counter electrode prepared in Example 13 of the present invention.
  • FIG. 11 is a photograph showing the results of XPS component analysis of the graphene compound prepared in Synthesis Example 2 of the present invention.
  • a method of manufacturing a graphene counter electrode for a dye-sensitized solar cell of the present invention includes the steps of: a) preparing a graphene compound doped with nitrogen element by doping nitrogen to graphite; And b) surface treating the graphene compound prepared in step a) to the FTO transparent electrode by using electrostatic spray deposition.
  • a graphene compound doped with nitrogen is prepared by doping nitrogen to graphite.
  • the method of doping the graphite with nitrogen but preferably, by increasing the dispersibility by modifying the surface of the graphite using PPA and P 2 O 5 , the dispersed graphite under nitrogen atmosphere
  • the graphene compound may be prepared by heat treatment to dope the nitrogen element.
  • the graphene compound can be prepared by modifying the surface of graphite under a nitrogen atmosphere using a ball milling method and simultaneously doping with nitrogen.
  • the preparation of the graphene compound by doping the nitrogen element is as in Figure 1 (a).
  • graphite (EFG) is formed in which an aminobenzoyl group is formed at an edge by reacting with poly (phosphate) / phosphorus pentoxide (P 2 O 5 ).
  • the EFG is extracted by Soxhlet extractions to minimize other variables.
  • the EFG powder is heat treated at 900 ° C. for 2 hours under a nitrogen atmosphere.
  • the 4-aminobenzoyl moiety (4-H 2 N-Ph-CO-) covalently attached to the edge of the EFG may be in an initial state to make the graphene compound during C-welding and N-doping.
  • Graphene compound doped with a nitrogen element of the present invention prepared as described above preferably comprises 1 to 15% by weight of the nitrogen element.
  • the nitrogen content is less than 1% by weight, there is a problem in the catalyst properties and stability.
  • the nitrogen content is more than 15% by weight, the effect of increasing the amount of nitrogen is not much increased.
  • Each of the graphene compounds prepared above may be dispersed in a generally used organic solvent, and may be deposited on an FTO / glass substrate using the graphene compound.
  • the electrostatic spray deposition Electrostatic Spray Deposition
  • the prepared graphene compound is surface-treated on an FTO transparent electrode by using an electrostatic spray electrodeposition method to prepare a counter electrode.
  • the electrospinning electrodeposition method is not particularly limited, but may preferably use the apparatus as shown in FIG. Looking at the manufacturing method of the graphene counter electrode of the present invention with Figure 2, the graphene compound prepared in the step is dispersed in 2-propanol, and then sprayed at a constant rate of about 200 ⁇ L / min under a high voltage of about 10 kV It is injected into capillaries.
  • the electric field overcomes the surface tension of each drop as a result of minimizing the numerous charged microdroplets containing the graphene compound.
  • the graphene compound doped with nitrogen element is deposited on the uniform FTO / glass substrate to the surface treatment of the FTO transparent electrode.
  • Surface treatment of the FTO transparent electrode is preferably carried out surface treatment for a time of 4 minutes to 9 minutes. 3 (a), 3 (b), 3 (c) and 3 (d) of the present invention, FIG. 3 (b) and FIG. 3 (d) subjected to surface treatment by the electrostatic radiation electrodeposition method.
  • the FTO transparent electrode of Fig. 3A is a counter electrode having a strong catalytic characteristic compared to the FTO transparent electrode of Figs. 3 (a) and 3 (c) without surface treatment.
  • the present invention also provides a graphene counter electrode for a dye-sensitized solar cell including a graphene compound doped with a nitrogen element.
  • the graphene counter electrode for dye-sensitized solar cells of the present invention includes a first electrode including a conductive transparent substrate; And a surface treatment layer including a graphene compound doped with nitrogen on the surface of the first electrode.
  • the first electrode including the conductive transparent substrate may be a glass substrate or a plastic substrate including a transmissive electrode so that the graphene compound doped with nitrogen may be surface treated by a radiation electrodeposition method.
  • the nitrogen-doped graphene surface layer serves to reduce an electrolyte having oxidation-reduction characteristics.
  • electrolyte examples include I ⁇ / I 3 ⁇ , a cobalt complex, and ferrocene.
  • the present invention provides a dye-sensitized solar cell including the graphene counter electrode.
  • a dye containing a graphene compound doped with nitrogen element is treated by surface treatment of the FTO transparent electrode so that the graphene compound doped with nitrogen element is deposited on a uniform FTO / glass substrate for 1 minute.
  • a graphene counter electrode for a sensitized solar cell was prepared. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.08 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 2 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.17 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 3 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.26 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 4 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.35 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 5 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.44 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 6 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.51 ⁇ m.
  • a dye containing a graphene compound doped with nitrogen element is treated by surface treatment of the FTO transparent electrode so that the graphene compound doped with nitrogen element is deposited on a uniform FTO / glass substrate for 1 minute.
  • a graphene counter electrode for a sensitized solar cell was prepared. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.08 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 2 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.17 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 3 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.26 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 4 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.35 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 5 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.44 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 6 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.51 ⁇ m.
  • a graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 7 minutes.
  • the thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.58 ⁇ m.
  • the thickness measurement of the graphene compound is shown in FIG. 9.
  • a Pt (platinum) counter electrode As a graphene counter electrode for a conventional dye-sensitized solar cell, a Pt (platinum) counter electrode was used.
  • a solution was prepared by mixing the following dye and co-adsorbed hole transport material molarity in ethanol solvent (6 mL).
  • a dye-sensitized solar cell was manufactured according to the following procedure.
  • the FTO glass substrate was placed in a sodium hydroxide cleaning solution, ultrasonically cleaned for 1 hour, washed with distilled water and ethanol, and dried using nitrogen gas.
  • the washed FTO glass substrate was immersed in a 40 mM TiCl 4 aqueous solution and heated in an oven at 70 ° C. for 30 minutes.
  • the TiCl 4 treated FTO glass substrate was washed with distilled water and ethanol, dried using nitrogen gas, and heated in an oven at 80 ° C. for 10 minutes.
  • a TiO 2 paste having a 13 nm particle size was coated on a TiCl 4 treated FTO glass substrate by a doctor blade method, and dried at room temperature (20 ° C.) for 2 hours.
  • TiO 2 coated FTO glass substrate was dried in an 80 ° C. oven for 2 hours.
  • the TiO 2 coated FTO glass substrate was baked at a maximum temperature of 500 ° C. for 30 minutes while gradually raising the temperature using a heating furnace.
  • the fired FTO glass substrate was coated with a TiO 2 paste having a particle size of 400 nm by a doctor blade method. And after drying for 2 hours at room temperature (20 °C), it was baked for 30 minutes at a maximum 500 °C while gradually raising the temperature using a heating furnace.
  • the calcined FTO glass substrate was immersed in 40mM TiCl 4 aqueous solution for 30 minutes, washed with distilled water and ethanol, dried using nitrogen gas, and dried at 80 ° C. for 10 minutes.
  • the dried FTO glass substrate was sintered using a heating gun for 30 minutes, and then dipping into a solution of O-alkylated-JK-225-sensitizer diluted to 0.3 mM prepared above.
  • the adsorbed dye and coadsorption transport material for 12 hours.
  • the dye-adsorbed FTO glass substrate was washed with ethanol and dried using nitrogen gas.
  • the FTO glass substrate was immersed in an aqueous solution of H 2 O / acetone / HCl (4: 4: 2, v / v / v%) for 1 hour, washed with an ultrasonic cleaner, and dried in an oven at 70 ° C. for 30 minutes. .
  • the anode and the cathode prepared above were coalesced using a hot press heated to 80 ° C. using a polymer sealing film.
  • the electrolyte prepared above was injected through the two holes and sealed with a sealing film and a cover glass.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 2.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 3.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 4.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 5.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 6.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 7.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was the counter electrode prepared in Example 8.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was the counter electrode prepared in Example 9.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was the counter electrode prepared in Example 10.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 11.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 12.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 13.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode used in Comparative Example 1.
  • the prepared transmittances of Examples 1 to 13 were measured and shown in FIGS. 5 (a) and 5 (b).
  • the transmittance of Example 1 using Synthesis Example 1 was the highest and that of Example 6 was the lowest.
  • the transmittance of Example 7 using Synthesis Example 2 was the highest and that of Example 13 was the lowest.
  • Example 14 Comparative Example 2 11.6 916 0.74 7.85
  • Example 14 9.32 913 0.55 4.66
  • Example 15 8.70 893 0.61 4.70
  • Example 16 11.2 916 0.69 7.07
  • Example 17 12.5 875 0.70 7.64
  • Example 18 12.4 896 0.72 8.01
  • Example 19 12.6 884 0.74 8.24
  • Example 20 12.77 877 0.67 7.55
  • Example 21 13.55 877 0.70 8.32
  • Example 22 13.69 886 0.71 8.67
  • Example 23 13.88 884 0.72 8.97
  • Example 24 14.07 889 0.74 9.31
  • Example 25 14.11 887 0.74 9.28
  • Example 26 14.01 889 0.74 9.25
  • VOC, J SC and Filter Factor of the solar cells of Examples 17 to 26 using the counter electrode according to the present invention were equivalent or superior to those of the solar cell of Comparative Example 2 using the conventional counter electrode. It can be seen that it has.

Abstract

The present invention relates to a graphene counter electrode for a dye-sensitized solar cell, a method for manufacturing same, and a dye-sensitized solar cell comprising same, the method comprising the steps of: a) manufacturing a graphene compound onto which nitrogen elements are doped by doping nitrogen on graphite; and b) surface-treating an FTO transparent electrode with the graphene compound manufactured in step a) by using electrostatic spray deposition.

Description

염료감응 태양전지용 그래핀 상대전극, 이의 제조방법 및 이를 포함하는 염료감응 태양전지Graphene counter electrode for dye-sensitized solar cell, manufacturing method thereof and dye-sensitized solar cell comprising same
본 발명은 염료감응 태양전지용 그래핀 상대전극, 이의 제조방법 및 이를 포함하는 염료감응 태양전지에 관한 것이다.The present invention relates to a graphene counter electrode for a dye-sensitized solar cell, a manufacturing method thereof, and a dye-sensitized solar cell including the same.
염료감응 태양전지의 원리는, 표면에 염료분자가 화학적으로 흡착된 n-형 나노입자 반도체 산화물 전극에 태양빛(가시광선)이 흡수되면 염료 분자가 전자-홀 쌍을 생성하고, 상기전자는 반도체 산화물의 전도띠로 주입되어 나노입자간 계면을 통하여 투명전도성 막으로 전달되어 전류를 발생시키며, 상기 홀은 산화-환원 전해질에 의해 전자를 받아 다시 환원되며 산화된 전해질이 상대전극으로 이동된 전자를 받아 다시 환원되는 것이다.The principle of dye-sensitized solar cells is that dye molecules generate electron-hole pairs when sunlight (visible light) is absorbed by n-type nanoparticle semiconductor oxide electrodes with dye molecules chemically adsorbed on the surface, and the electrons are semiconductor It is injected into the conduction band of the oxide and is transferred to the transparent conductive film through the interface between nanoparticles to generate a current. The hole receives electrons by the redox electrolyte and is reduced again, and the oxidized electrolyte receives electrons moved to the counter electrode. It is reduced again.
현재까지 염료감응 태양전지에 사용되는 상대전극 물질로는 예를 들어, WO98/050393에서와 같이 주로 Pt(platinum)를 사용하였지만, 상기 Pt를 사용하는 경우에는 산화-환원 전해질에 의한 반응으로 인한 부식성으로 인한 안정성이 약하며, 특히 Pt의 가격이 높기 때문에 경제성이 떨어진다는 문제점이 있었다. 따라서, 이러한 문제점을 극복할 수 있는 새로운 상대전극 물질에 대한 개발의 필요성이 요구되고 있다.As a counter electrode material used in dye-sensitized solar cells to date, mainly Pt (platinum) is used as in, for example, WO98 / 050393. However, when Pt is used, corrosiveness due to a reaction by an oxidation-reducing electrolyte is used. Due to the weak stability, in particular, because of the high price of Pt there was a problem that the economy is poor. Therefore, there is a need for the development of a new counter electrode material that can overcome this problem.
본 발명은 기존에 사용해오던 Pt(platinum) 상대전극보다 장기안정성, 촉매 특성이 매우 우수한 염료감응 태양전지용 그래핀 상대전극 및 이의 제조방법을 제공함에 그 목적이 있다.It is an object of the present invention to provide a graphene counter electrode for a dye-sensitized solar cell having excellent long-term stability and catalytic properties than a conventional Pt (platinum) counter electrode, and a method of manufacturing the same.
상술한 목적을 달성하기 위하여, In order to achieve the above object,
본 발명은 a) 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조하는 단계; 및 b) 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명 전극에 표면 처리하는 단계를 포함하는 염료감응 태양전지용 그래핀 상대전극의 제조방법을 제공한다.The present invention comprises the steps of: a) preparing a graphene compound doped with nitrogen elements by doping nitrogen to graphite; And b) surface treating the graphene compound prepared in step a) to an FTO transparent electrode by using an electrostatic spray deposition method. do.
또한, 본 발명은 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제공한다.The present invention also provides a graphene counter electrode for a dye-sensitized solar cell including a graphene compound doped with a nitrogen element.
또한, 본 발명은 상기 그래핀 상대전극을 포함하는 염료감응 태양전지를 제공한다.In addition, the present invention provides a dye-sensitized solar cell including the graphene counter electrode.
상기 과제의 해결 수단에 따른 본 발명의 그래핀 상대전극을 포함하는 염료감응 태양전지는 장기안정성, 촉매 특성이 기존의 Pt 상대전극을 이용한 태양전지에 비하여 매우 우수하다.Dye-sensitized solar cell comprising a graphene counter electrode of the present invention according to the solution of the above problem is very excellent in long-term stability, catalyst characteristics compared to the conventional solar cell using a Pt counter electrode.
도 1(a)은 본 발명의 합성예 1의 그래핀 화합물 제조단계를 모식화하여 나타낸 도면이다.Figure 1 (a) is a diagram schematically showing the production step of the graphene compound of Synthesis Example 1 of the present invention.
도 1(b)은 본 발명의 합성예 2의 그래핀 화합물 제조단계를 모식화하여 나타낸 도면이다.Figure 1 (b) is a diagram schematically showing the production step of the graphene compound of Synthesis Example 2 of the present invention.
도 2는 본 발명의 상대전극을 제조하는 단계를 모식화하여 나타낸 도면이다.2 is a view schematically illustrating a step of manufacturing a counter electrode of the present invention.
도 3(a)는 FTO 표면 상태를 나타낸 사진이다.Figure 3 (a) is a photograph showing the FTO surface state.
도 3(b)는 본 발명의 합성예 1에서 제조한 그래핀을 FTO 투명전극에 정전 방사 전착법으로 표면처리한 후의 상태를 나타낸 사진이다.Figure 3 (b) is a photograph showing the state after the surface treatment of the graphene prepared in Synthesis Example 1 of the present invention to the FTO transparent electrode by the electrostatic radiation electrodeposition method.
도 3(c)는 FTO 표면 상태를 확대하여 나타낸 사진이다.Fig. 3 (c) is an enlarged photograph of the FTO surface state.
도 3(d)는 본 발명의 합성예 2에서 제조한 그래핀을 FTO 투명전극에 정전 방사 전착법으로 표면처리한 후의 상태를 나타낸 사진이다.Figure 3 (d) is a photograph showing the state after surface treatment of the graphene prepared in Synthesis Example 2 of the present invention to the FTO transparent electrode by the electrostatic radiation electrodeposition method.
도 4(a)는 본 발명의 실시예 1 내지 실시예 6에서 제조한 상대 전극을 나타낸 사진이다.4 (a) is a photograph showing the counter electrode manufactured in Examples 1 to 6 of the present invention.
도 4(b)는 본 발명의 실시예 7 내지 실시예 13에서 제조한 상대 전극의 표면을 나타낸 사진이다.4 (b) is a photograph showing the surface of the counter electrode manufactured in Examples 7 to 13 of the present invention.
도 5(a)는 본 발명의 실시예 1 내지 실시예 6에서 제조한 상대전극의 투과도를 나타낸 그래프이다.5 (a) is a graph showing the transmittance of the counter electrode prepared in Examples 1 to 6 of the present invention.
도 5(b)는 본 발명의 실시예 7 내지 실시예 13에서 제조한 상대전극의 투과도를 나타낸 그래프이다.5 (b) is a graph showing the transmittance of the counter electrode prepared in Examples 7 to 13 of the present invention.
도 6(a)은 본 발명의 실시예 1 내지 실시예 6 및 비교예 1에서 제조한 상대전극의 촉매특성을 측정한 그래프이다.6 (a) is a graph measuring the catalyst characteristics of the counter electrode prepared in Examples 1 to 6 and Comparative Example 1 of the present invention.
도 6(b)은 본 발명의 실시예 7 내지 실시예 13 및 비교예 1에서 제조한 상대전극의 촉매특성을 측정한 그래프이다.6 (b) is a graph measuring the catalyst characteristics of the counter electrode prepared in Examples 7 to 13 and Comparative Example 1 of the present invention.
도 7(a)은 본 발명의 실시예 1 내지 실시예 6 및 비교예 1에서 제조한 상대전극의 안정성을 측정한 그래프이다.7 (a) is a graph measuring the stability of the counter electrode prepared in Examples 1 to 6 and Comparative Example 1 of the present invention.
도 7(b)은 본 발명의 실시예 7 내지 실시예 13 및 비교예 1에서 제조한 상대전극의 안정성을 측정한 그래프이다.7 (b) is a graph measuring the stability of the counter electrode prepared in Examples 7 to 13 and Comparative Example 1 of the present invention.
도 8(a)은 본 발명의 실시예 14 내지 실시예 19 및 비교예 2에서 제조한 상대전극의 전류-전압 곡선을 측정한 그래프이다.8 (a) is a graph measuring current-voltage curves of the counter electrodes manufactured in Examples 14 to 19 and Comparative Example 2 of the present invention.
도 8(b)은 본 발명의 실시예 20 내지 실시예 26 및 비교예 2에서 제조한 상대전극의 전류-전압 곡선을 측정한 그래프이다.FIG. 8B is a graph measuring current-voltage curves of the counter electrodes manufactured in Examples 20 to 26 and Comparative Example 2 of the present invention.
도 9는 본 발명의 실시예 13에서 제조한 상대전극의 그래핀 화합물의 enRP를 측정한 사진이다.9 is a photograph of the enRP of the graphene compound of the counter electrode prepared in Example 13 of the present invention.
도 10은 본 발명의 합성예 1에서 제조한 그래핀 화합물을 XPS 성분분석한 결과를 나타낸 사진이다.10 is a photograph showing the results of XPS component analysis of the graphene compound prepared in Synthesis Example 1 of the present invention.
도 11은 본 발명의 합성예 2에서 제조한 그래핀 화합물을 XPS 성분분석한 결과를 나타낸 사진이다.11 is a photograph showing the results of XPS component analysis of the graphene compound prepared in Synthesis Example 2 of the present invention.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 염료감응 태양전지용 그래핀 상대전극의 제조방법은 a) 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조하는 단계; 및 b) 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명 전극에 표면처리하는 단계를 포함한다. A method of manufacturing a graphene counter electrode for a dye-sensitized solar cell of the present invention includes the steps of: a) preparing a graphene compound doped with nitrogen element by doping nitrogen to graphite; And b) surface treating the graphene compound prepared in step a) to the FTO transparent electrode by using electrostatic spray deposition.
본 발명의 염료감응 태양전지용 그래핀 상대전극을 제조하기 위해서, 먼저 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조한다. 본 발명에 있어서, 상기 그래파이트에 질소를 도핑하는 방법으로는 특별한 제한은 없으나, 바람직하게는 PPA와 P2O5를 이용하여 그래파이트의 표면을 개질함으로써 분산력을 높인 후, 분산된 그래파이트에 질소 분위기 하에서 열처리하여 질소 원소를 도핑시켜 그래핀 화합물을 제조할 수 있다. 또한 그래파이트에서 질소를 도핑하는 다른 방법으로 ball milling방식으로 질소 분위기하에서 그래파이트의 표면을 ball mill사용하여 개질함과 동시에 질소가 도핑시켜 그래핀 화합물을 제조 할 수 있다. 구체적으로, 상기 질소 원소를 도핑시켜 그래핀 화합물의 제조는 도 1(a)에서와 같다. 먼저 순수한 그래파이트의 가장자리 부분에서 선택적인 작용이 수행된다. 이 후, 4-아미노벤조산(4-aminobenzoic acid)의 존재하에서 폴리(인산)/오산화인(P2O5)와 반응하여 가장자리부분에 아미노벤조일기가 형성된 그래파이트(EFG)가 형성한다. 상기 EFG는 다른 변수를 최소화 하기 위하여, 속슬레 추출(Soxhlet extractions)에 의하여 추출한다. 상기 EFG 파우더는 질소 분위기하에서 900℃에서 2시간동안 열처리한다. 열처리하는 동안, EFG의 가장자리에 공유결합된 4-아미노벤조일 부분(4-H2N-Ph-CO-)은 C-용접 및 N-도핑 동안 그래핀 화합물을 만들기 위하여 초기 상태로 있을 수 있다.In order to manufacture the graphene counter electrode for a dye-sensitized solar cell of the present invention, first, a graphene compound doped with nitrogen is prepared by doping nitrogen to graphite. In the present invention, there is no particular limitation as to the method of doping the graphite with nitrogen, but preferably, by increasing the dispersibility by modifying the surface of the graphite using PPA and P 2 O 5 , the dispersed graphite under nitrogen atmosphere The graphene compound may be prepared by heat treatment to dope the nitrogen element. In addition, as another method of doping nitrogen in graphite, the graphene compound can be prepared by modifying the surface of graphite under a nitrogen atmosphere using a ball milling method and simultaneously doping with nitrogen. Specifically, the preparation of the graphene compound by doping the nitrogen element is as in Figure 1 (a). First, an optional action is performed on the edge of pure graphite. Thereafter, in the presence of 4-aminobenzoic acid, graphite (EFG) is formed in which an aminobenzoyl group is formed at an edge by reacting with poly (phosphate) / phosphorus pentoxide (P 2 O 5 ). The EFG is extracted by Soxhlet extractions to minimize other variables. The EFG powder is heat treated at 900 ° C. for 2 hours under a nitrogen atmosphere. During the heat treatment, the 4-aminobenzoyl moiety (4-H 2 N-Ph-CO-) covalently attached to the edge of the EFG may be in an initial state to make the graphene compound during C-welding and N-doping.
또한 그래파이트에서 질소를 도핑하는 다른 방법으로는 도 1(b)에서와 같다.In addition, another method of doping nitrogen in the graphite is as in Figure 1 (b).
스텐레스 캡슐안을 질소 분위기하에서 순수한 그래파이트와 5mm지름의 ball mill을 500 RPM속도로 교반시켜 줌으로써 순수한 그래파이트가 깨지면서 활성 라디칼이 생성되어 질소가 쉽게 도핑되는 원리를 이용하였다. In a stainless steel capsule, pure graphite and a 5 mm diameter ball mill were stirred at 500 RPM in a nitrogen atmosphere, and thus, pure graphite was broken and active radicals were generated, thus easily doping nitrogen.
상기와 같이 제조되는 본 발명의 질소 원소가 도핑된 그래핀화합물은 질소 원소를 1~15 중량% 포함하는 것이 바람직하다. 질소 원소가 1 중량% 미만으로 포함되는 경우 촉매특성 및 안정성에 문제가 있으며, 질소 원소가 15 중량% 초과로 포함되었을 경우에는 질소량 증가에 따른 효과의 증가가 별로 없다. Graphene compound doped with a nitrogen element of the present invention prepared as described above preferably comprises 1 to 15% by weight of the nitrogen element. When the nitrogen content is less than 1% by weight, there is a problem in the catalyst properties and stability. When the nitrogen content is more than 15% by weight, the effect of increasing the amount of nitrogen is not much increased.
상기 제조된 각각의 그래핀 화합물은 일반적으로 사용되는 유기 용제에 분산될 수 있으며, 이를 이용하여 FTO/유리기판에 증착시킬 수 있다. 종래의 스핀코팅을 이용하는 경우에는 두께, 형태 및 균일성을 제어하기 어렵다는 문제가 있었으나 본 발명에서는 이러한 문제점을 해결하기 위하여, 다음과 같이 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하였다.Each of the graphene compounds prepared above may be dispersed in a generally used organic solvent, and may be deposited on an FTO / glass substrate using the graphene compound. In the case of using the conventional spin coating, there is a problem that it is difficult to control the thickness, shape and uniformity, but in the present invention, in order to solve the problem, the electrostatic spray deposition (Electrostatic Spray Deposition) was used as follows.
본 발명의 염료감응 태양전지용 그래핀 상대전극을 제조하기 위해서, 이 후, 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 제조된 그래핀 화합물을 FTO 투명 전극에 표면 처리하여 상대전극을 제조한다. 상기 정전 방사 전착법은 특별한 제한은 없으나, 바람직하게는 도 2와 같은 장치를 이용할 수 있다. 본 발명의 그래핀 상대전극의 제조방법을 도 2와 함께 살펴보면, 상기 단계에서 제조된 그래핀 화합물은 2-프로판올에 분산된 후, 약 10 kV의 높은 전압하에서 약 200μL/min의 일정한 속도로 분사 모세 혈관에 주입된다. 전기장은 상기 그래핀 화합물을 포함하는 전하를 띤 수많은 미세 방울들을 최소화한 결과로 각 방울의 표면 장력을 극복하게 된다. 이를 통하여, 질소 원소가 도핑된 그래핀화합물이 균일한 FTO/유리 기판 상에 증착되어 FTO 투명 전극의 표면처리를 하게 된다. 상기 FTO 투명 전극에 표면처리하는 단계는 4분 내지 9분의 시간으로 표면처리를 하는 것이 바람직하다. 본 발명의 도 3(a), 도 3(b), 도 3(c), 도 3(d)를 비교해 보면, 정전 방사 전착법으로 표면처리를 한 도 3(b)와 도 3(d)의 FTO 투명 전극은 표면처리를 하지 않은 도 3(a), 도 3(c) 의 FTO 투명 전극에 비하여 강한 촉매특성을 지닌 상대전극이 된다.In order to manufacture the graphene counter electrode for a dye-sensitized solar cell of the present invention, thereafter, the prepared graphene compound is surface-treated on an FTO transparent electrode by using an electrostatic spray electrodeposition method to prepare a counter electrode. . The electrospinning electrodeposition method is not particularly limited, but may preferably use the apparatus as shown in FIG. Looking at the manufacturing method of the graphene counter electrode of the present invention with Figure 2, the graphene compound prepared in the step is dispersed in 2-propanol, and then sprayed at a constant rate of about 200μL / min under a high voltage of about 10 kV It is injected into capillaries. The electric field overcomes the surface tension of each drop as a result of minimizing the numerous charged microdroplets containing the graphene compound. Through this, the graphene compound doped with nitrogen element is deposited on the uniform FTO / glass substrate to the surface treatment of the FTO transparent electrode. Surface treatment of the FTO transparent electrode is preferably carried out surface treatment for a time of 4 minutes to 9 minutes. 3 (a), 3 (b), 3 (c) and 3 (d) of the present invention, FIG. 3 (b) and FIG. 3 (d) subjected to surface treatment by the electrostatic radiation electrodeposition method. The FTO transparent electrode of Fig. 3A is a counter electrode having a strong catalytic characteristic compared to the FTO transparent electrode of Figs. 3 (a) and 3 (c) without surface treatment.
또한, 본 발명은 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제공한다.The present invention also provides a graphene counter electrode for a dye-sensitized solar cell including a graphene compound doped with a nitrogen element.
구체적으로 본 발명의 염료감응 태양전지용 그래핀 상대전극은 전도성 투명 기판을 포함하는 제1전극; 및 상기 제1전극 표면에 질소가 도핑된 그래핀 화합물을 포함하는 표면처리 층을 포함한다.Specifically, the graphene counter electrode for dye-sensitized solar cells of the present invention includes a first electrode including a conductive transparent substrate; And a surface treatment layer including a graphene compound doped with nitrogen on the surface of the first electrode.
상기 염료감응 태양전지용 그래핀 상대전극을 구성하는 소재들을 예를 들어 설명하면 다음과 같다. Referring to the materials constituting the graphene counter electrode for the dye-sensitized solar cell, for example.
먼저 전도성 투명 기판을 포함하는 제1전극은 질소가 도핑된 그래핀 화합물을 방사 전착법에 의하여 표면처리 할 수 있도록, 투광성 전극을 포함하는 유리 기판 또는 플라스틱 기판일 수 있다. First, the first electrode including the conductive transparent substrate may be a glass substrate or a plastic substrate including a transmissive electrode so that the graphene compound doped with nitrogen may be surface treated by a radiation electrodeposition method.
상기 질소가 도핑된 그래핀 표면층은 산화-환원 특성을 갖는 전해질을 환원 시켜주는 작용을 하는데, 상기 전해질로써는 I-/I3 -, 코발트 착화합물, 페로센 등이 있다.The nitrogen-doped graphene surface layer serves to reduce an electrolyte having oxidation-reduction characteristics. Examples of the electrolyte include I − / I 3 − , a cobalt complex, and ferrocene.
또한, 본 발명은 상기 그래핀 상대전극을 포함하는 염료감응 태양전지를 제공한다.In addition, the present invention provides a dye-sensitized solar cell including the graphene counter electrode.
이하, 실시예를 통해 본 발명을 구체적으로 설명한다. 그러나, 이러한 실시예는 본 발명을 좀 더 명확하게 설명하기 위하여 제시되는 것일 뿐, 본 발명의 범위를 제한하는 목적으로 제시되는 것은 아니다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.Hereinafter, the present invention will be described in detail through examples. However, these examples are only presented to explain the present invention more clearly, and are not intended to limit the scope of the present invention. The scope of the invention will be defined by the technical spirit of the claims below.
그래핀 화합물의 제조Preparation of Graphene Compounds
[합성예 1]Synthesis Example 1
순수한 그래파이트(Aldrich Chemicals 사 제품) 0.5g와 4-아미노벤조산(4-aminobenzoic acid) 0.5g을 섞은 후, 여기에 PPA(83% P2O5 assay: 20.0 g)/오산화인(P2O5) 5.0g을 넣은 후, 이를 130℃에서 72시간 교반하였다. 이 후, 생성된 화합물을 속슬레 추출(Soxhlet extractions)에 의하여 추출한 후, 생성된 화합물을 질소 분위기하에서 900℃에서 2시간 동안 열처리하여, 질소 원소가 도핑된 그래핀 화합물을 제조하였다. 상기 그래핀 화합물 내의 질소함량을 XPS 분석법을 이용하여 측정하여 도 9에 나타내었으며, 그래핀 화합물의 구성비는 탄소(C) 95.16%, 질소(N) 1.73%, 산소(O) 1.78% 이었다.After mixing 0.5 g of pure graphite (manufactured by Aldrich Chemicals) and 0.5 g of 4-aminobenzoic acid, PPA (83% P 2 O 5 assay: 20.0 g) / phosphorus pentoxide (P 2 O 5 ) 5.0 g was added thereto, followed by stirring at 130 ° C. for 72 hours. Thereafter, the resultant compound was extracted by Soxhlet extractions, and the resultant compound was heat-treated at 900 ° C. for 2 hours under a nitrogen atmosphere to prepare a graphene compound doped with nitrogen. The nitrogen content in the graphene compound was measured using XPS analysis, and is shown in FIG. 9. The composition ratio of the graphene compound was 95.16% of carbon (C), 1.73% of nitrogen (N), and 1.78% of oxygen (O).
[합성예 2]Synthesis Example 2
스텐레스로 이루어진 캡슐에 지름 5mm 스텐레스 ball을 넣고 순수한 그래파이트(Aldrich Chemicals 사 제품) 5g과 8 bar압력에 해당되는 질소가스를 주입하여 밀봉하고 5200 RPM속도로 48시간동한 교반하였다. 이 후, 생성된 화합물을 1M HCl을 이용하여 세척하여주고 세척된 화합물을 0.05 mmHg 압력으로 -120℃ 로 48시간 동한 냉건조 시켜주어 질소 원소가 도핑된 그래핀 화합물을 제조하였다. 상기 그래핀 화합물 내의 질소함량을 XPS 분석법을 이용하여 측정하여 도 9에 나타내었으며, 그래핀 화합물의 구성비는 탄소(C) 70.67%, 질소(N) 14.84%, 산소(O) 7.43%, 수소(H) 0.79% 이었다.5mm diameter stainless steel ball was put into a stainless steel capsule, and 5 g of pure graphite (manufactured by Aldrich Chemicals Co., Ltd.) and nitrogen gas corresponding to 8 bar pressure were injected and sealed, and stirred for 48 hours at a speed of 5200 RPM. Thereafter, the resultant compound was washed with 1M HCl, and the washed compound was cooled and dried at −120 ° C. for 48 hours at 0.05 mmHg pressure to prepare a graphene compound doped with nitrogen. The nitrogen content in the graphene compound was measured using XPS analysis, and is shown in FIG. 9. The composition ratio of the graphene compound was 70.67% of carbon (C), 14.84% of nitrogen (N), 7.43% of oxygen (O), and hydrogen ( H) 0.79%.
상대전극의 제조Preparation of counter electrode
[실시예 1]Example 1
상기 합성예 1을 사용하여 질소 원소가 도핑된 그래핀 화합물을 2-프로판올에 분산시킨 후, 10 kV의 전압하에서 200μL/min의 일정한 속도로 분사 모세 혈관에 주입시켰다. Using Synthesis Example 1, the graphene compound doped with nitrogen element was dispersed in 2-propanol, and then injected into the injection capillaries at a constant rate of 200 μL / min under a voltage of 10 kV.
이 후, 전기장을 가한 후, 1분간 질소 원소가 도핑된 그래핀화합물이 균일한 FTO/유리 기판 상에 증착되도록 FTO 투명 전극의 표면처리를 하여, 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.08 μm 이었다.Subsequently, after applying an electric field, a dye containing a graphene compound doped with nitrogen element is treated by surface treatment of the FTO transparent electrode so that the graphene compound doped with nitrogen element is deposited on a uniform FTO / glass substrate for 1 minute. A graphene counter electrode for a sensitized solar cell was prepared. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.08 μm.
[실시예 2]Example 2
상기 FTO 투명 전극의 표면처리를 2분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.17 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 2 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.17 μm.
*[실시예 3][Example 3]
상기 FTO 투명 전극의 표면처리를 3분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.26 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 3 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.26 μm.
[실시예 4]Example 4
*상기 FTO 투명 전극의 표면처리를 4분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.35 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 4 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.35 μm.
[실시예 5]Example 5
상기 FTO 투명 전극의 표면처리를 5분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.44 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 5 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.44 μm.
[실시예 6]Example 6
상기 FTO 투명 전극의 표면처리를 6분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.51 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the surface treatment of the FTO transparent electrode was performed for 6 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.51 μm.
[실시예 7]Example 7
상기 합성예 2를 사용하여 질소 원소가 도핑된 그래핀 화합물을 2-프로판올에 분산시킨 후, 10 kV의 전압하에서 200μL/min의 일정한 속도로 분사 모세 혈관에 주입시켰다. Using Synthesis Example 2, the graphene compound doped with nitrogen was dispersed in 2-propanol, and then injected into the injection capillaries at a constant rate of 200 μL / min under a voltage of 10 kV.
이 후, 전기장을 가한 후, 1분간 질소 원소가 도핑된 그래핀화합물이 균일한 FTO/유리 기판 상에 증착되도록 FTO 투명 전극의 표면처리를 하여, 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.08 μm 이었다.Subsequently, after applying an electric field, a dye containing a graphene compound doped with nitrogen element is treated by surface treatment of the FTO transparent electrode so that the graphene compound doped with nitrogen element is deposited on a uniform FTO / glass substrate for 1 minute. A graphene counter electrode for a sensitized solar cell was prepared. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.08 μm.
[실시예 8]Example 8
상기 FTO 투명 전극의 표면처리를 2분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.17 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 2 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.17 μm.
[실시예 9]Example 9
상기 FTO 투명 전극의 표면처리를 3분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.26 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 3 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.26 μm.
[실시예 10]Example 10
상기 FTO 투명 전극의 표면처리를 4분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.35 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 4 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.35 μm.
[실시예 11]Example 11
상기 FTO 투명 전극의 표면처리를 5분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.44 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 5 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.44 μm.
*[실시예 12][Example 12]
상기 FTO 투명 전극의 표면처리를 6분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.51 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 6 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.51 μm.
[실시예 13]Example 13
상기 FTO 투명 전극의 표면처리를 7분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.58 μm 이었다. 상기 그래핀 화합물의 두께 측정을 도 9에 나타내었다.A graphene counter electrode for a dye-sensitized solar cell was manufactured in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 7 minutes. The thickness of the graphene compound of the graphene counter electrode for the dye-sensitized solar cell was 0.58 μm. The thickness measurement of the graphene compound is shown in FIG. 9.
[비교예 1]Comparative Example 1
종래의 염료감응 태양전지용 그래핀 상대전극으로 Pt(platinum) 상대전극을 사용하였다.As a graphene counter electrode for a conventional dye-sensitized solar cell, a Pt (platinum) counter electrode was used.
상기 제조된 실시예 1 내지 13의 염료감응 태양전지용 그래핀 상대전극을 도 4(a), 도 4(b)에 나타내었다.The graphene counter electrode for the dye-sensitized solar cell of Examples 1 to 13 prepared above is shown in FIGS. 4 (a) and 4 (b).
염료 용액 제조 Dye solution preparation
에탄올 용매 (6mL)에 다음과 같은 염료 및 공흡착 정공수송물질 몰농도로 혼합하여 용액를 제조하였다.A solution was prepared by mixing the following dye and co-adsorbed hole transport material molarity in ethanol solvent (6 mL).
0.3m몰(M) 농도의 O-alkylated-JK-225-sensitizer 염료 용매O-alkylated-JK-225-sensitizer dye solvent at 0.3 mmol (M) concentration
30m몰(M) 농도의 DCA 용매DCA solvent at 30 mmol (M) concentration
전해질 제조Electrolyte manufacturing
Co(bpy)3(BCN4)2을 0.22 몰(M), Co(bpy)3(BCN4)3을 0.05 몰(M), LiClO4를 0.1 몰(M) 및 4-tert-butylpyridine을 0.8 몰(M) 첨가하여 아세토나이트릴 전해질(2 mL)을 제조하였다. Co (bpy) 3 (BCN 4 ) 2 to 0.22 molar (M), Co (bpy) 3 (BCN 4) 3 0.05 molar (M), LiClO 4 to a 0.1 molar (M) and 4-tert-butylpyridine 0.8 Molar (M) was added to prepare acetonitrile electrolyte (2 mL).
염료감응 태양전지의 제조 Manufacture of Dye-Sensitized Solar Cell
[실시예 14]Example 14
다음의 공정에 따라 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured according to the following procedure.
1. FTO 유리기판을 수산화나트륨 세정용액에 넣고 1시간 동안 초음파 세척한 후, 증류수와 에탄올을 이용하여 세척하고, 질소가소를 이용해 건조시켰다.1. The FTO glass substrate was placed in a sodium hydroxide cleaning solution, ultrasonically cleaned for 1 hour, washed with distilled water and ethanol, and dried using nitrogen gas.
2. 세척된 FTO 유리기판을 40mM 농도의 TiCl4 수용액에 담근 후에 70℃ 오븐에서 30분간 가열하였다.2. The washed FTO glass substrate was immersed in a 40 mM TiCl 4 aqueous solution and heated in an oven at 70 ° C. for 30 minutes.
3. TiCl4 처리된 FTO 유리기판을 증류수와 에탄올을 이용하여 세척한 후, 질소 가스를 이용하여 건조시키고, 80℃ 오븐에서 10분간 가열하였다.3. The TiCl 4 treated FTO glass substrate was washed with distilled water and ethanol, dried using nitrogen gas, and heated in an oven at 80 ° C. for 10 minutes.
4. 이어서, TiCl4 처리된 FTO 유리기판에 13nm 입자 크기의 Ti02 페이스트를 닥터 블레이드(doctor blade) 방법으로 코팅하고, 상온에서(20℃) 2시간 동안 건조시켰다.4. Then, a TiO 2 paste having a 13 nm particle size was coated on a TiCl 4 treated FTO glass substrate by a doctor blade method, and dried at room temperature (20 ° C.) for 2 hours.
5. Ti02가 코팅된 FTO 유리기판을 80℃ 오븐에서 2시간 동안 건조시켰다.5. TiO 2 coated FTO glass substrate was dried in an 80 ° C. oven for 2 hours.
6. 이어서, Ti02가 코팅된 FTO 유리기판을 가열로를 이용하여 서서히 온도를 올리면서 최대 500℃에서 30분간 소성시켰다.6. Subsequently, the TiO 2 coated FTO glass substrate was baked at a maximum temperature of 500 ° C. for 30 minutes while gradually raising the temperature using a heating furnace.
7. 상기 소성된 FTO 유리기판을 입자크기 400nm인 Ti02 페이스트를 닥터 블레이드 방법으로 코팅하였다. 그리고 상온에서(20℃) 2시간 동안 건조시킨 후, 가열로를 이용하여 서서히 온도를 올리면서 최대 500℃에서 30분간 소성시켰다.7. The fired FTO glass substrate was coated with a TiO 2 paste having a particle size of 400 nm by a doctor blade method. And after drying for 2 hours at room temperature (20 ℃), it was baked for 30 minutes at a maximum 500 ℃ while gradually raising the temperature using a heating furnace.
8. 이어서, 상기 소성된 FTO 유리기판을 40mM TiCl4 수용액에 30분 동안 담근 후, 증류수와 에탄올을 이용하여 세척하고 질소가스를 이용하여 건조시키고, 80℃ 오븐에서 10분 동안 건조하였다.8. Subsequently, the calcined FTO glass substrate was immersed in 40mM TiCl 4 aqueous solution for 30 minutes, washed with distilled water and ethanol, dried using nitrogen gas, and dried at 80 ° C. for 10 minutes.
9. 이어서, 상기 건조된 FTO 유리기판을 히팅건(heating gun)을 이용하여 30분 동안 소결한 후에 상기에서 제조된 0.3mM로 희석된 O-alkylated-JK-225-sensitizer의 용액에 딥핑(dipping)하여 12시간 동안 염료와 공흡착 전공수송물질을 흡착시켰다. 9. Subsequently, the dried FTO glass substrate was sintered using a heating gun for 30 minutes, and then dipping into a solution of O-alkylated-JK-225-sensitizer diluted to 0.3 mM prepared above. The adsorbed dye and coadsorption transport material for 12 hours.
*10. 상기 염료가 흡착된 FTO 유리기판을 에탄올로 세척한 후, 질소가스를 이용하여 건조시켰다.* 10. The dye-adsorbed FTO glass substrate was washed with ethanol and dried using nitrogen gas.
11. FTO 유리기판(상대전극용)에 전해질을 주입하기 위한 지름 0.6mm의 두개 구멍을 뚫었다.11. Two holes 0.6 mm in diameter were made to inject the electrolyte into the FTO glass substrate (for the counter electrode).
12. 이어서, FTO 유리기판을 H2O/아세톤/HCl(4:4:2, v/v/v%) 수용액에 1시간 동안 담가서 초음파 세척기로 세척하고, 70℃ 오븐에서 30분 동안 건조시켰다.12. Subsequently, the FTO glass substrate was immersed in an aqueous solution of H 2 O / acetone / HCl (4: 4: 2, v / v / v%) for 1 hour, washed with an ultrasonic cleaner, and dried in an oven at 70 ° C. for 30 minutes. .
13. 이어서, 실시예 1에서 제조된 FTO 상대전극을 준비한다.13. Next, the FTO counter electrode prepared in Example 1 was prepared.
14. 상기에서 제조된 산화전극과 환원전극을 고분자 실링 필름(sealing film)을 이용하여 80℃로 가열된 핫프레스(hot press)를 이용하여 합체하였다.14. The anode and the cathode prepared above were coalesced using a hot press heated to 80 ° C. using a polymer sealing film.
15. 상기 두개 구멍을 통하여 상기에서 제조된 전해질을 주입하고 실링필름과 커버 글래스(cover glass)로 밀봉하였다.15. The electrolyte prepared above was injected through the two holes and sealed with a sealing film and a cover glass.
[실시예 15]Example 15
상기 FTO 상대전극을 실시예 2에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 2.
[실시예 16]Example 16
상기 FTO 상대전극을 실시예 3에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 3.
[실시예 17]Example 17
상기 FTO 상대전극을 실시예 4에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 4.
[실시예 18]Example 18
상기 FTO 상대전극을 실시예 5에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 5.
[실시예 19]Example 19
상기 FTO 상대전극을 실시예 6에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 6.
[실시예 20]Example 20
상기 FTO 상대전극을 실시예 7에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 7.
[실시예 21]Example 21
상기 FTO 상대전극을 실시예 8에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was the counter electrode prepared in Example 8.
[실시예 22]Example 22
상기 FTO 상대전극을 실시예 9에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was the counter electrode prepared in Example 9.
[실시예 23]Example 23
상기 FTO 상대전극을 실시예 10에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was the counter electrode prepared in Example 10.
[실시예 24]Example 24
상기 FTO 상대전극을 실시예 11에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 11.
[실시예 25]Example 25
상기 FTO 상대전극을 실시예 12에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 12.
[실시예 26]Example 26
상기 FTO 상대전극을 실시예 13에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode prepared in Example 13.
[비교예 2]Comparative Example 2
상기 FTO 상대전극을 비교예 1에서 사용한 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured in the same manner as in Example 14, except that the FTO counter electrode was used as the counter electrode used in Comparative Example 1.
실험예 1: 염료감응 태양전지 상대전극의 투과도 측정Experimental Example 1 Measurement of Permeability of Dye-Sensitized Solar Cell Counter Electrode
상기 제조된 실시예 1 내지 실시예 13의 투과도를 측정하여 도 5(a), 도 5(b)에 나타내었다. 합성예 1을 이용한 실시예 1의 투과도가 가장 높았으며 실시예 6의 투과도가 가장 낮았다. 합성예 2를 이용한 실시예 7의 투과도가 가장 높았고 실시예 13의 투과도가 가장 낮았다.The prepared transmittances of Examples 1 to 13 were measured and shown in FIGS. 5 (a) and 5 (b). The transmittance of Example 1 using Synthesis Example 1 was the highest and that of Example 6 was the lowest. The transmittance of Example 7 using Synthesis Example 2 was the highest and that of Example 13 was the lowest.
실험예 2: 염료감응 태양전지 상대전극의 촉매특성 측정Experimental Example 2 Measurement of Catalyst Characteristics of Dye-Sensitized Solar Cell Counter Electrode
상기 합성예 1을 이용한 실시예 1 내지 실시예 6 및 비교예 1의 상대전극의 촉매 특성의 확인하기 위하여, dummy cell을 제작하여 전해질에 대한 산화-환원 전류값을 측정하였다. 측정된 결과를 도6(a)에 나타내었다. 상기 합성예 2를 이용한 실시예 7 내지 실시예 13 및 비교예 1의 상대전극의 촉매 특성을 같은 방법으로 측정하여 도 6(b)에 나타내었다. 이를 통하여 실시예 4 내지 실시예 6의 경우, 비교예 1(기존의 Pt 상대전극)보다 촉매적 특성이 우수하다는 것을 확인할 수 있었고, 실시예 7 내지 실시예 13의 경우, 비교예 1(기존의 Pt 상대전극)보다 촉매적 특성이 우수하다는 것을 확인하였다.In order to confirm the catalytic properties of the counter electrodes of Examples 1 to 6 and Comparative Example 1 using Synthesis Example 1, a dummy cell was fabricated to measure the oxidation-reduction current value for the electrolyte. The measured results are shown in Fig. 6 (a). The catalytic properties of the counter electrodes of Examples 7 to 13 and Comparative Example 1 using Synthesis Example 2 were measured and shown in FIG. 6 (b). As a result, in Examples 4 to 6, it was confirmed that the catalytic properties are superior to Comparative Example 1 (conventional Pt counter electrode), and in Examples 7 to 13, Comparative Example 1 (conventional It was confirmed that the catalytic property is superior to that of the Pt counter electrode).
실험예 3: 염료감응 태양전지 상대전극의 안정성 측정Experimental Example 3: Measurement of stability of dye-sensitized solar cell counter electrode
실시예 6의 상대전극과 비교예 1의 상대전극의 안정성을 측정하기 위해서 dummy cell 을 제작하여, 다음과 같이 연속적으로 각각의 상대전극에 전압을 연속적으로 가하여 (0 V → 1 V → -1 V → 0 V) 안정성을 테스트하였다. 측정된 테스트 결과를 도 7에 나타내었다. 이를 통하여 실시예 6의 상대전극이 비교예 1(기존의 Pt 상대전극)보다 내부저항 크기가 작음을 확인하여 안정성이 우수함을 확인할 수 있었다. 또한 실시예 12의 상대전극과 비교예 1의 상대전극을 상기와 같은 방법으로 안정성을 테스트하여 실시예 12의 상대전극이 비교예 1보다 내부저항 크기가 작음을 확인하여 안정성이 우수함을 확인하였다.In order to measure the stability of the counter electrode of Example 6 and the counter electrode of Comparative Example 1, a dummy cell was fabricated, and voltage was continuously applied to each counter electrode as follows (0 V → 1 V → −1 V). → 0 V) Stability was tested. The measured test results are shown in FIG. 7. As a result, it was confirmed that the counter electrode of Example 6 had a smaller internal resistance than that of Comparative Example 1 (the existing Pt counter electrode), thereby confirming excellent stability. In addition, the stability of the counter electrode of Example 12 and the counter electrode of Comparative Example 1 was tested in the same manner as described above to confirm that the counter electrode of Example 12 had a smaller internal resistance than that of Comparative Example 1, and thus the stability was excellent.
실험예 4: 염료감응 태양전지의 성능 평가Experimental Example 4: Performance Evaluation of Dye-Sensitized Solar Cell
실시예 14 내지 실시예 26 및 비교예 2에서 제조한 각각의 염료감응 태양전지를 사용하여 1 sun(100 mW/cm2) 일루미네이션(illumination) 조건에서 광전류-전압을 측정하여 그 결과를 도 8(a), 8(b) 및 하기 표 1에 나타내었다. Each dye-sensitized solar cell prepared in Examples 14 to 26 and Comparative Example 2 was used to measure the photocurrent-voltage under 1 sun (100 mW / cm 2 ) illumination conditions, and the results are shown in FIG. a), 8 (b) and Table 1 below.
표 1
JSC(mA/cm2) VOC(mV) FF PCE(%)
비교예 2 11.6 916 0.74 7.85
실시예 14 9.32 913 0.55 4.66
실시예 15 8.70 893 0.61 4.70
실시예 16 11.2 916 0.69 7.07
실시예 17 12.5 875 0.70 7.64
실시예 18 12.4 896 0.72 8.01
실시예 19 12.6 884 0.74 8.24
실시예 20 12.77 877 0.67 7.55
실시예 21 13.55 877 0.70 8.32
실시예 22 13.69 886 0.71 8.67
실시예 23 13.88 884 0.72 8.97
실시예 24 14.07 889 0.74 9.31
실시예 25 14.11 887 0.74 9.28
실시예 26 14.01 889 0.74 9.25
Table 1
J SC (mA / cm 2 ) V OC (mV) FF PCE (%)
Comparative Example 2 11.6 916 0.74 7.85
Example 14 9.32 913 0.55 4.66
Example 15 8.70 893 0.61 4.70
Example 16 11.2 916 0.69 7.07
Example 17 12.5 875 0.70 7.64
Example 18 12.4 896 0.72 8.01
Example 19 12.6 884 0.74 8.24
Example 20 12.77 877 0.67 7.55
Example 21 13.55 877 0.70 8.32
Example 22 13.69 886 0.71 8.67
Example 23 13.88 884 0.72 8.97
Example 24 14.07 889 0.74 9.31
Example 25 14.11 887 0.74 9.28
Example 26 14.01 889 0.74 9.25
상기에서와 같이, 본 발명에 의한 상대전극을 사용한 실시예 17 내지 26의 태양전지의 VOC, JSC 및 Filter Factor가 종래의 상대전극을 사용한 비교예 2의 태양전지에 비하여 동등 또는 우위의 성능을 갖는 것을 알 수 있다.As described above, the VOC, J SC and Filter Factor of the solar cells of Examples 17 to 26 using the counter electrode according to the present invention were equivalent or superior to those of the solar cell of Comparative Example 2 using the conventional counter electrode. It can be seen that it has.

Claims (7)

  1. a) 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조하는 단계; 및a) preparing a graphene compound doped with nitrogen element by doping nitrogen to graphite; And
    b) 정전 방사 전착법(Electronic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명전극에 표면처리하는 단계를 포함하는 염료감응 태양전지용 그래핀 상대전극의 제조방법.b) a method of manufacturing a graphene counter electrode for a dye-sensitized solar cell, comprising surface treating the graphene compound prepared in step a) on an FTO transparent electrode by using an electrospray electrodeposition method.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 FTO 투명 전극에 표면처리하는 단계는 4분 내지 9분간 표면처리를 하는 것을 특징으로 하는 염료감응 태양전지용 그래핀 상대전극의 제조방법.Surface treatment of the FTO transparent electrode is a method of manufacturing a graphene counter electrode for a dye-sensitized solar cell, characterized in that the surface treatment for 4 minutes to 9 minutes.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 FTO 투명 전극에 표면처리하는 단계는 FTO 투명 전극에 증착된 그래핀 화합물의 두께가 0.1 내지 0.6μm가 되도록 표면처리하는 것을 특징으로 하는 염료감응 태양전지용 그래핀 상대전극의 제조방법.The surface treatment of the FTO transparent electrode is a method of manufacturing a graphene counter electrode for a dye-sensitized solar cell, characterized in that the surface treatment so that the thickness of the graphene compound deposited on the FTO transparent electrode is 0.1 to 0.6μm.
  4. 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극.Graphene counter electrode for dye-sensitized solar cell comprising a graphene compound doped with nitrogen element.
  5. 청구항 4에 있어서,The method according to claim 4,
    상기 그래핀 화합물은 질소 원소를 1~15 중량% 포함하는 것을 특징으로 하는 염료감응 태양전지용 그래핀 상대전극.The graphene compound is a graphene counter electrode for a dye-sensitized solar cell, characterized in that containing 1 to 15% by weight of a nitrogen element.
  6. 청구항 4에 있어서, 상기 염료감응 태양전지용 그래핀 상대전극은The graphene counter electrode of claim 4, wherein the dye-sensitized solar cell
    전도성 투명 기판을 포함하는 제1전극; 및A first electrode comprising a conductive transparent substrate; And
    상기 제1전극 표면에 질소가 도핑된 그래핀 화합물의 두께가 0.1 내지 0.6μm인 표면처리 층을 포함하는 것을 특징으로 하는 염료감응 태양전지용 그래핀 상대전극.The graphene electrode for a dye-sensitized solar cell comprising a surface treatment layer having a thickness of 0.1 to 0.6μm thickness of the graphene compound doped with nitrogen on the surface of the first electrode.
  7. 청구항 4의 그래핀 상대전극을 포함하는 염료감응 태양전지.Dye-sensitized solar cell comprising the graphene counter electrode of claim 4.
PCT/KR2014/000629 2013-01-25 2014-01-22 Graphene counter electrode for dye-sensitized solar cell, method for manufacturing same, and dye-sensitized solar cell comprising same WO2014116026A1 (en)

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US11415540B2 (en) * 2019-03-05 2022-08-16 Abb Schweiz Ag Technologies using nitrogen-functionalized pseudo-graphite
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