WO2019132620A1 - Couche tampon pour cellule solaire à colorant et cellule solaire à colorant - Google Patents

Couche tampon pour cellule solaire à colorant et cellule solaire à colorant Download PDF

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Publication number
WO2019132620A1
WO2019132620A1 PCT/KR2018/016925 KR2018016925W WO2019132620A1 WO 2019132620 A1 WO2019132620 A1 WO 2019132620A1 KR 2018016925 W KR2018016925 W KR 2018016925W WO 2019132620 A1 WO2019132620 A1 WO 2019132620A1
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WIPO (PCT)
Prior art keywords
layer
dye
buffer layer
electrode
solar cell
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PCT/KR2018/016925
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English (en)
Korean (ko)
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김영미
김종복
백종규
신규순
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주식회사 동진쎄미켐
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Publication of WO2019132620A1 publication Critical patent/WO2019132620A1/fr

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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
    • 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

Definitions

  • the present invention relates to a dye-sensitized solar cell and a counter electrode for a dye-sensitized solar cell, and more particularly, to a buffer layer and a dye-sensitized solar cell including the buffer layer, which can prevent the catalyst layer of the second electrode from being deteriorated by the dye.
  • the dye-sensitized solar cell has advantages of higher photoelectric conversion efficiency and lower manufacturing cost than other cells.
  • a dye is adsorbed on a semiconductor oxide layer, and excited electrons are injected into a semiconductor oxide to be driven.
  • the adsorption between the dye and the semiconductor oxide layer is carried out using a deposition method.
  • the main mechanism of adsorption is the chemical bond between the anchoring group (-COOH) of the dye and the semiconductor oxide (eg, TiO 2 ), but also a large number of physical bonds due to aggregation between the dyes.
  • Embodiments of the present invention provide a buffer layer for a dye-sensitized solar cell that can prevent the dropped dye from reacting with the catalyst layer on the second electrode to induce the removal of the catalyst layer.
  • Another embodiment of the present invention provides a dye-sensitized solar cell including a buffer layer for a dye-sensitized solar cell, which can prevent the dropped dye from reacting with the catalyst layer on the second electrode to induce the removal of the catalyst layer .
  • a dye-sensitized solar cell includes a first electrode, a photoelectric conversion layer, a second electrode including a catalyst layer, and an electrolyte interposed between the first electrode and the second electrode, And a buffer layer interposed between the layer and the catalyst layer and composed of one or more layers including a pore and conductive carbon.
  • the second electrode includes a buffer layer that can move the electrolyte while blocking the movement of the dye, thereby preventing deterioration of the catalyst layer.
  • FIG. 1 is a cross-sectional view of a dye-sensitized solar cell according to an embodiment
  • the buffer layer is formed of a mixed layer of a metal oxide and a conductive carbon
  • 3A is a perspective view showing a case where a buffer layer is formed by sequentially laminating a conductive carbon layer and a metal oxide layer,
  • FIG. 3B is a perspective view showing a case where the buffer layer is formed by sequentially laminating a metal oxide layer and a conductive carbon layer,
  • FIG. 3C is a perspective view showing a case where the buffer layer is formed by sequentially laminating a conductive carbon layer, a metal oxide layer, and a conductive carbon layer,
  • FIG. 4 is a perspective view showing a case where the buffer layer is formed of conductive carbon
  • 5 is a graph showing a fill factor with time.
  • FIG. 1 is a partial cross-sectional view of a dye-sensitized solar cell according to an embodiment.
  • the cell includes a first electrode 11, a photoelectric conversion layer 13, a second electrode 31, an electrolyte (not shown) disposed in a space between the first electrode 11 and the second electrode 31 20 and a buffer layer 33.
  • the first electrode 11 is formed by forming a conductive layer 11b on one surface of the first electrode substrate 11a.
  • the first electrode substrate 11a various materials such as glass and plastic can be used.
  • the plastic a plate-like or film-like plastic composed of a cycloolefin-based polymer, an acrylic urea-based polymer, polyester, polyethylene naphthalate or the like can be used. If plastic is used for the first electrode substrate 11a, a flexible dye-sensitized solar cell can be realized.
  • the conductive layer 11b may be formed of ITO (indium-tin composite oxide), FTO (fluorine-doped tin oxide), or the like.
  • the photoelectric conversion layer 13 may be composed of a dye 13b adsorbed to the semiconductor material 13a.
  • the dye 13b is a material capable of absorbing visible light to generate an electron-hole pair.
  • the terminal group of the dye 13b is not specifically limited, but specifically includes a carboxyl group (-COOH), a cyanoacrylic acid group, Alkoxysilyl group, pyridine group, phosphonic acid group, tetracyanate group, perylene dicarboxylic acid anhydride group, 2-hydroxybenzoyl group, (2-hydroxybenzonitrile), 8-hydroxylquinoline group, pyridine-N-oxide group, hydroxylpyridium group, catechol group, A hydroxamate, a sulfonic acid, an acetylacetanate, a boronic acid, a nitro, a tetrazole, a rhodamine, and salicylic acid.
  • the dye (13b) may be a metal complex dye or an organic dye.
  • the metal complex dyes include ruthenium complexes containing a bipyridine structure, a terpyridine structure and the like in a ligand, metal complexes such as polypyrin and phthalocyanine, and examples thereof include the following chemical formula.
  • organic dyes include organic dyes such as eosin, rhodamine, and melochene.
  • organic dyes such as eosin, rhodamine, and melochene.
  • MK2, MK14, D102, D149, Y123, JK2, C220, DPP07, DPP13 and the like can be used as the organic dyes in detail.
  • the semiconductor material 13a may be formed of a material that transmits generated electrons.
  • the semiconductor material 13a include oxide semiconductors such as TiO 2 , SnO 2 , ZnO, WO 3 , Nb 2 O 5 , In 2 O 3 , ZrO 2 , Ta 2 O 5 and TiSrO 3 ; Sulfide semiconductors such as CdS, ZnS, In 2 S, PbS, Mo 2 S, WS 2, Sb 2 S 3 , Bi 2 S 3 , ZnCdS 2 and CuS 2 ; Metal chalcogenides such as CdSe, In 2 Se 2 , WSe 2 , PbSe, and CdTe; Element semiconductors such as GaAs, Si, Se and InP, and the like.
  • a composite of two or more kinds of these materials such as a complex of SnO 2 and ZnO, a composite of TiO 2 and Nb 2 O 5 It is possible.
  • the kind of semiconductors is not limited to these, and two or more kinds of semiconductors may be mixed and used. Of these, oxides of Ti, Zn, Sn and Nb are preferable, and TiO 2 is particularly preferable.
  • a material having an average particle diameter of 10 nm or more and 1 ⁇ ⁇ or less can be suitably used for the semiconductor material 13a. Materials having different average particle diameters may be mixed, or particles having a single particle diameter may be used.
  • the photoelectric conversion layer 13 may be referred to as a working electrode together with the first electrode 11.
  • the electrolyte (20) may be any of liquid, solid, coagulated, and room temperature molten salt.
  • the electrolyte 20 contains an iodine / iodide ion or a redox pair such as a bromine / bromide ion
  • the semiconductor material 13a is preferably formed of a material which does not cause deterioration due to the oxidation reaction.
  • the second electrode 31 is formed by forming a catalyst layer 31b on the second electrode substrate 31a.
  • the second electrode substrate 31a can be formed of various materials such as glass and plastic.
  • the plastic a plate-like or film-like plastic composed of a cycloolefin-based polymer, an acrylic urea-based polymer, polyester, polyethylene naphthalate or the like can be used.
  • the second electrode substrate 31a may be made of the same material as that of the first electrode substrate 11a, or may be formed using another material.
  • the catalyst layer 31b is formed on the second electrode substrate 31a with a metal such as platinum (Pt) or a conductive polymer or carbon to prepare the second electrode 31. [ The catalyst layer 31b functions to reduce the electrolyte 20.
  • the buffer layer 33 is interposed between the electrolyte 20 and the catalyst layer 31b.
  • the buffer layer 33 prevents the dye 13b floating off the electrolyte 20 from contacting with the catalyst layer 31b of the second electrode 31 to react.
  • the buffer layer 33 may have an appropriate porosity. Accordingly, the redox pair (e.g., I 3 - / I - ) of the electrolyte 20 can move to the buffer layer, but the dye 13 b can not move through the buffer layer and the catalyst layer 31b) and the dye.
  • the redox pair e.g., I 3 - / I -
  • the buffer layer 33 should have a pore size such that the redox pair (eg, I 3 - / I - ) of the electrolyte 20 passes through but the dye 13 b can not pass through.
  • the pore size may be between 0.5 and 500 nm.
  • the pore size may be 0.5 to 5 nm in size. If the size of the pore is 0.5 nm or less, the migration of the redox pair (e.g., I 3 - / I - ) is hindered and the filling rate is lowered.
  • the size of the pore is 500 nm or more, So that the possibility of direct contact between the catalyst layer 31b and the dye is increased.
  • the thickness of the buffer layer 33 may be sufficient to provide a sufficient barrier function to the dye 13b while enabling bi-directional movement of the redox pair (e.g., I 3 - / I - ) of the electrolyte 20, And may be 10 nm to 10 ⁇ or less. Preferably, the thickness may be 0.5 to 5 mu m. When the thickness of the buffer layer 33 is 10 nm or less, the possibility of direct contact between the dye 13b and the catalyst layer 31b of the second electrode may be increased. When the thickness of the buffer layer 33 is 10 m or more, (Eg, I 3 - / I - ) of the redox couple, and the filling rate is lowered.
  • the pore size and the thickness of the buffer layer 33 are complementary to each other. Even if the pore size is small, the thickness of the pore is reduced even though the pore size is small, So that the reaction does not occur.
  • the buffer layer 33 is formed of a mixed layer 233 of a conductive carbon and a metal oxide, A two-layered film in which a conductive carbon layer 333a and a metal oxide layer 333b are sequentially formed on the catalyst layer 31b as shown in FIG. 3B, and a metal oxide layer The conductive carbon layer 333a and the conductive carbon layer 333a are sequentially formed on the catalyst layer 31b as shown in FIG.
  • Layered film such as a three-layer film in which a metal oxide layer 333c is sequentially formed, as shown in FIG. 4, may be formed.
  • TiO 2 , SiO 2 , Al 2 O 3 , Nb 2 O 5 , ZrO 2 , WO 3, ZnO, MgO, SnO 2 , such as a single metal oxide or a Nb-TiO 2 of, Zr-TiO 2, Sn- TiO 2, Zn-TiO 2, Mg-TiO 2 , such as the like of two or more mixed metal oxide can be used have.
  • the conductive carbon graphene, graphite, graphen oxide, carbon nanotubes, carbon black and the like can be used.
  • TiO 2 paste (having an average particle diameter of 18 nm, manufactured by Dongjin Semichem Co., Ltd.) was printed on the FTO glass, and then baked at 450 ° C for 30 minutes to form a semiconductor layer having a thickness of about 4 ⁇ m.
  • the organic dye (MK2) was then dissolved in ethanol at 0.5 mM to obtain a dye solution.
  • To the resulting dye solution was added TiO 2
  • the layered FTO glass was supported for 12 hours and then washed with ethanol to prepare a working electrode.
  • a Pt paste (manufactured by Dongjin Semichem Co., Ltd.) was printed on the FTO glass and then fired at 450 ° C for 30 minutes to form a second electrode having a catalyst layer. Then, a mixed paste of metal oxide (TiO 2 ) and graphene was printed on the catalyst layer to a thickness of 5 ⁇ m and then baked to form a buffer layer composed of a single layer of a mixed layer of metal oxide and conductive carbon.
  • TiO 2 metal oxide
  • graphene graphene
  • a Pt paste (manufactured by Dongjin Semichem Co., Ltd.) was printed on the FTO glass and then fired at 450 ° C for 30 minutes to form a second electrode having a catalyst layer.
  • a carbon graphene layer was formed on the catalyst layer to a thickness of 2.5 ⁇
  • a metal oxide (TiO 2 ) layer was formed thereon to a thickness of 2.5 ⁇
  • a conductive carbon layer and a metal oxide layer were sequentially stacked to form a two- Thereby forming a buffer layer.
  • a Pt paste (manufactured by Dongjin Semichem Co., Ltd.) was printed on the FTO glass and then fired at 450 ° C for 30 minutes to form a second electrode having a catalyst layer.
  • a graphene layer was formed as a conductive carbon layer on the catalyst layer to a thickness of 5 mu m to form a buffer layer composed of a single layer of the conductive carbon layer.
  • a Pt paste (manufactured by Dongjin Semichem Co., Ltd.) was printed on the FTO glass and then fired at 450 ° C for 30 minutes to form a second electrode having a catalyst layer.
  • no buffer layer was formed separately on the catalyst layer.
  • a Pt paste (manufactured by Dongjin Semichem Co., Ltd.) was printed on the FTO glass and then fired at 450 ° C for 30 minutes to form a second electrode having a catalyst layer. Then, a 5 ⁇ thick metal oxide (TiO 2 ) monolayer was formed on the catalyst layer to form a buffer layer composed of a single layer of the metal oxide layer.
  • the buffer layer is formed of a mixed layer of a metal oxide and a conductive carbon (Experimental Example 1)
  • a two-layer film in which a conductive carbon layer and a metal oxide layer are laminated (Experimental Example 2)
  • the metal oxide layer is formed on the conductive carbon layer and the metal oxide layer is in contact with the electrolyte, the reduction rate of the filling rate is remarkably high at 2.7%.
  • the buffer layer is formed of a two-layered film including a metal oxide layer and a conductive carbon layer according to Experimental Example 2, the complexity of the pores formed in the buffer layer increases and the effect is remarkable.
  • the fabricated dye-sensitized solar cell module was fabricated in the same manner as described above, except that the thickness of the buffer layer was different, and the reduction rate of the filling rate after 1000 hours at 85 ° C was measured.
  • MOx represents the metal oxide layer.
  • the thickness of the buffer layer was formed to be 5 ⁇ ⁇ to make the pore size different from that of the dye-sensitized solar cell module manufactured in the same manner as described above, and then the rate of reduction of the filling rate after 1000 hours was measured under the condition of 85 ⁇ ⁇ , 3.
  • pore size was measured using the BET method.
  • the present invention is applicable to a dye-sensitized solar cell.

Abstract

L'invention concerne une cellule solaire à colorant capable d'empêcher la dégradation d'un facteur de remplissage et d'améliorer le rendement. La cellule solaire à colorant comprend une contre-électrode, qui comprend, sur une couche de catalyseur sur un substrat, une couche tampon capable de bloquer le mouvement du colorant tout en permettant le mouvement d'un électrolyte, ce qui permet d'empêcher la détérioration de la couche de catalyseur.
PCT/KR2018/016925 2017-12-29 2018-12-28 Couche tampon pour cellule solaire à colorant et cellule solaire à colorant WO2019132620A1 (fr)

Applications Claiming Priority (2)

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KR1020170184765A KR20190081906A (ko) 2017-12-29 2017-12-29 염료 감응 태양 전지용 버퍼층 및 염료 감응 태양 전지
KR10-2017-0184765 2017-12-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080052082A (ko) * 2006-12-07 2008-06-11 한국전자통신연구원 전자 재결합 차단층을 포함하는 염료감응 태양전지 및 그제조 방법
KR20090020058A (ko) * 2007-08-22 2009-02-26 한국전자통신연구원 전자 재결합 차단층을 포함하는 염료감응 태양전지 및 그제조 방법
KR20120036655A (ko) * 2010-10-08 2012-04-18 주식회사 상보 차단층을 포함하는 염료감응태양전지
KR20140047244A (ko) * 2012-10-11 2014-04-22 주식회사 동진쎄미켐 염료감응 태양전지 모듈 및 그 제조 방법
KR101406427B1 (ko) * 2013-05-02 2014-06-17 학교법인 포항공과대학교 우수한 촉매활성도와 전기전도도를 갖는 염료 감응형 태양전지용 전도성 고분자-탄소 복합체 전극과 이를 이용한 염료 감응형 태양전지 및 이들의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080052082A (ko) * 2006-12-07 2008-06-11 한국전자통신연구원 전자 재결합 차단층을 포함하는 염료감응 태양전지 및 그제조 방법
KR20090020058A (ko) * 2007-08-22 2009-02-26 한국전자통신연구원 전자 재결합 차단층을 포함하는 염료감응 태양전지 및 그제조 방법
KR20120036655A (ko) * 2010-10-08 2012-04-18 주식회사 상보 차단층을 포함하는 염료감응태양전지
KR20140047244A (ko) * 2012-10-11 2014-04-22 주식회사 동진쎄미켐 염료감응 태양전지 모듈 및 그 제조 방법
KR101406427B1 (ko) * 2013-05-02 2014-06-17 학교법인 포항공과대학교 우수한 촉매활성도와 전기전도도를 갖는 염료 감응형 태양전지용 전도성 고분자-탄소 복합체 전극과 이를 이용한 염료 감응형 태양전지 및 이들의 제조방법

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