WO2000054361A1 - Dispositifs de conversion photoelectrique fabriques au moyen d'electrolytes etheres - Google Patents

Dispositifs de conversion photoelectrique fabriques au moyen d'electrolytes etheres Download PDF

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Publication number
WO2000054361A1
WO2000054361A1 PCT/JP2000/001379 JP0001379W WO0054361A1 WO 2000054361 A1 WO2000054361 A1 WO 2000054361A1 JP 0001379 W JP0001379 W JP 0001379W WO 0054361 A1 WO0054361 A1 WO 0054361A1
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WO
WIPO (PCT)
Prior art keywords
formula
photoelectric conversion
compound
electrolyte
conversion element
Prior art date
Application number
PCT/JP2000/001379
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English (en)
Japanese (ja)
Inventor
Takaaki Sakai
Shouhei Matsui
Katsuhito Miura
Masanori Yanagida
Original Assignee
Daiso Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daiso Co., Ltd. filed Critical Daiso Co., Ltd.
Priority to JP2000604485A priority Critical patent/JP4538955B2/ja
Publication of WO2000054361A1 publication Critical patent/WO2000054361A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • H01G9/2004—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

Definitions

  • the present invention relates to a photoelectric conversion element using an electrolyte of an ether compound having high ionic conductivity.
  • electrolytes in which iodine and potassium iodide are added to an organic solvent such as carbonate and tetrahydrofuran have been proposed as ion conductors for photoelectric conversion elements used for solar cells.
  • these electrolytes have a high vapor pressure and hinder the durability of the photoelectric conversion element.
  • durability of 10 years or more is required, and ion conductivity, An electrolyte with excellent safety and seal stability is desired.
  • the present inventors have proposed that a redox couple (B) composed of a combination of iodine and an iodine compound or a combination of bromine and a bromine compound is added to an ether compound (I), (11), (III) or (IV): (A). ) Can be obtained to obtain a desired electrolyte. Further, the inventors have found that this electrolyte is useful for application to a photoelectric conversion element such as a solar cell, and completed the present invention. That is, the present invention provides a photoelectric conversion element having excellent long-term stability by using an electrolyte having sufficient ion conductivity and excellent stability.
  • the present invention provides a photoelectric conversion element having excellent long-term stability by using an electrolyte having sufficient ion conductivity and excellent stability.
  • R 13 , R 14 , R 15 , R 16 , R 10 R 102 , R 103 , R 104 , and R 105 are a hydrogen atom or -0 A 1 (where A 1 is an alkyl group or an alkenyl group, and a is 1 to 12).
  • a 1 is an alkyl group or an alkenyl group, and a is 1 to 12.
  • R 10 ⁇ R 1Q5 are hydrogen atoms at the same time.
  • a photoelectric conversion element using an electrolyte comprising:
  • FIG. 1 is a cross-sectional view of the photoelectric conversion element obtained in Example 4.
  • the total number of ethylene oxide units (_CH 2 CH 2 0—) in the ether compound is:! -20, for example, 3-12.
  • R 17 , R 18 and R 19 are groups selected from an alkyl group having 1 to 6 carbon atoms or an alkyl group having 2 to 6 carbon atoms. 1, m and n are 0-12. However, all of 1, m and n are not 0 at the same time. ]
  • the sum of 1 + m + n is preferably 2 or more, and more preferably 3 or more.
  • the method for synthesizing the ether compound represented by the formula (II-1) having the structural formula of the formula (II) is as follows.
  • R 2. And R 2 R 22 and R 23 are groups selected from an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. o, p, q, r, s are 0-12. However, all of o, p, q, r, and s cannot be 0 at the same time. ]
  • the sum of o + p + q + r + s is preferably 2 or more, more preferably 3 or more, for example, 4 or more.
  • the alcohols of (e) and (f) are synthesized.
  • R 24 , R 25 , R 26 and R 27 are groups selected from an alkyl group having 1 to 6 carbon atoms or a alkenyl group having 2 to 6 carbon atoms.
  • t, u, v, w are 0-12. However, t, u, v, and w are not all 0 at the same time.
  • the sum of t + u + v + w is preferably 2 or more, more preferably 3 or more, for example, 4 or more.
  • the ether compound of the formula (II) can be obtained by the same operation as described above.
  • the redox couple ( ⁇ ) in the present invention is a pair of compounds that perform a reversible redox reaction, and when acid and reductants are independently added to the system, an electrochemical equilibrium is quickly reached.
  • Means a substance that A redox couple is a combination of an iodine-iodine compound or a combination of a bromine-bromine compound.
  • Iodine - ® ⁇ redox couple of a combination of iodine compounds for example, I 2 and L i I, Na I, KI , C s I, combinations of metal iodides such as Ca 1 2 or 1 2 and ⁇ Rukiruan, It is preferably composed of a combination of an iodine salt of a quaternary ammonium compound such as monodimodide and pyridinumodide or a high molecular compound having these in a side chain.
  • the redox couple of the combination of bromine one bromine compound for example, B r 2 and L i B r, N a B r, KB r, C s B r, C a B r 2 of a metal such as a bromide,, B r 2 And a quaternary ammonium compound such as alkylammonium bromide and pyridium bromide, or a high molecular weight compound having a side chain thereof.
  • the mixing ratio of the redox couple can be arbitrarily selected with the ether compound to be mixed. come. In general, an electrolyte having higher ionic conductivity can be obtained as the amount of the redox couple increases. However, if the mixing amount is too large, the dissociation of ions becomes difficult to occur, and the conductivity decreases. If the equilibrium potential of the redox couple is a problem, the mixing amount can be adjusted to obtain the required equilibrium potential.
  • the amount of the redox couple may be 1 to 50 parts by weight, for example, 5 to 35 parts by weight, based on 100 parts by weight of the ether compound.
  • the molar ratio of iodine: iodine compound (and bromine: bromine compound) in the redox couple is preferably 1: 5 to 5: 1.
  • the method for producing the electrolyte of the present invention is not particularly limited, but usually, it is sufficient that the ether compound (A) and the redox couple (B) can be mixed.
  • the method of mixing the redox couple (B) with the ether compound (A) is not particularly limited.
  • the method of directly mixing the redox couple (B) with the ether compound (A), the organic containing the redox couple (B) There is a method of mixing an ether compound (A) with a solvent.
  • the organic solvent is removed after the production of the electrolyte using an organic solvent (eg, acetonitrile).
  • a photoelectric conversion element is an element that converts photoenergy into electric energy by utilizing an electrochemical reaction between electrodes.
  • the photoelectric conversion element When the photoelectric conversion element is irradiated with light, electrons are generated at one electrode and move to the counter electrode through an electric wire provided between the electrodes.
  • the electrons transferred to the counter electrode reduce a redox couple in the electrolyte comprising the ether compound of the present invention.
  • the reduced redox couple travels from one electrode to the other as an anion in the electrolyte made of the ether compound, reaches the other electrode, and returns itself to the oxidized body, thereby transferring the electron to the other.
  • the photoelectric conversion element of the present invention is an element or a sensor that can convert light energy into electric energy. It also has a function as an optical sensor because it responds to light.
  • the photoelectric conversion element has an ether compound electrolyte and a pair (two) of electrodes.
  • Examples of the electrode include a conductor attached to a glass plate (a transparent protective material that transmits light).
  • a glass plate having electrodes is a glass plate coated with a conductive material (for example, a metal, an oxide semiconductor, particularly indium-tin oxide (ITO)). Good.
  • Oxide semiconductors such as titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanate, potassium titanate, potassium tantalate, tungsten oxide, iron oxide, cadmium sulfide, CdTe, C
  • a semiconductor such as silicon, a lid, cyan, polychenylene, polypyrrole, or polyaniline, or a material obtained by sensing the above-mentioned oxide semiconductor or semiconductor with a dye or other inorganic substance is supported. A more preferable photoelectric conversion element is obtained.
  • the photoelectric conversion element of the present invention includes an electrolyte made of an ether compound, one electrode containing a semiconductor (for example, an n-type semiconductor or a p-type semiconductor), and a semiconductor (for example, a p-type semiconductor or an n-type semiconductor). Alternatively, it may have one counter electrode made of metal.
  • An oxide semiconductor is preferable as the semiconductor to be supported on the electrode, and titanium oxide or titanium oxide sensitized with a dye is particularly preferable in terms of stability, safety, and price.
  • Dyes include organometallic complexes, for example, ruthenium-biviridine complexes, especially cis-di (thiocyanato) -N, N'-bis (2,2'-biviridyl-4,4'-dicarbonic acid) noretium (II ) (cis-di (thiocyanato) - N, N '- bis (2, 2' - bipyridyl-4, 4 '-dicarboxyl ic acicD rutheniunn, II)) provided on the electrode that force monkey 0 electrolytes use Rereru the
  • ruthenium-biviridine complexes especially cis-di (thiocyanato) -N, N'-bis (2,2'-biviridyl-4,4'-d
  • the photoelectric conversion element When the electrolyte of the ether compound of the present invention is used for a photoelectric conversion element, the photoelectric conversion element has excellent ion conductivity and excellent stability, so that a photoelectric conversion element having good conversion efficiency can be obtained. .
  • the photoelectric conversion element of the present invention can be used as a solar cell, an optical sensor, or the like.
  • FIG. 1 is a cross-sectional view of the photoelectric conversion element obtained in Example 4.
  • the photoelectric conversion element has glass plates 1 and 6, electrodes 2 and 5, a semiconductor layer 3, and an electrolyte layer 4 of an ether compound.
  • the transparent glass plates 1 and 6 protect the photoelectric conversion element and transmit light.
  • the thickness of the glass plates 1 and 6 may be 0.1-5 mm.
  • Electrode 2 is transparent IT O (indium monotin oxide) may be used. The thickness of the electrode 2 may be between 2 and 100 / m.
  • Layer 3 is made of porous Ti 2 and emits holes and electrons from light.
  • the electrolyte layer 4 is composed of an athenole compound and an electrolyte compound, and functions as a carrier layer for ions. The thickness of the electrolyte layer 4 may be between 5 and 1 000 / m.
  • Electrode 5 is preferably made of a metal (eg, gold and platinum). The thickness of the electrode 5 may be between 2 and 100 m.
  • the side surface of the photoelectric conversion element is sealed with resin 7.
  • resin ⁇ are an epoxy resin and an acrylic resin.
  • a lead wire 8 is connected to the electrodes 2 and 5.
  • Lead 8 is attached to electrodes 2 and 5 by a conductive paste (not shown).
  • the conductive paste include a silver paste and a power paste.
  • the properties of the ether compound were measured as follows.
  • Ionic conductivity (conductivity ⁇ ) was determined by complex impedance measurement. The measurement was performed using an alternating current method at 40 ° C, a voltage of 10 mV, and a frequency of 5 Hz to 13 MHz.
  • the 1,3-bis [2- (2-methoxyethoxy) ethoxy] obtained in Step 1 was added to 100 g (0.34 monole) of propanol and 20.4 g of NaOH (pellet) in the form of pellets. 51 mol), and 48.2 g (0.51 mol) of 2-chloroethyl methyl ether was added dropwise little by little while stirring at 60 ° C. After completion of the dropwise addition, the mixture was stirred for about 2 hours.
  • Ether compound prepared in Synthesis Example 2 (ii) lg, mixed lithium iodide 40 Omg ⁇ beauty iodine 10 Omg, was 8. 2 X10- 3 S "cm was measured ionic conductivity.
  • Ether compound prepared in Synthesis Example 3 (iii) was measured in the same manner Ion conductivity as in Example 2, 9. 2 X10- 3 S, was cm.
  • the nonwoven fabric was impregnated with the electrolyte compound, and then exposed to an iodine atmosphere for 2 hours.
  • Titanium oxide suspended on a transparent glass plate (glass plate thickness: 2 mm, ITO film thickness: 20 ⁇ m) coated with ITO (indium monotin oxide) by sputtering as a counter electrode. Apply a suspension, dry, and sinter to form a porous titanium oxide film
  • the light response of the current was measured by irradiating light of 96 WZm 2 with a solar simulator of AM I.5 as the light 3 ⁇ 4g.
  • a photoelectric conversion element having a semiconductor layer 3 and an electrolyte layer 4 using an ether compound (ii) and using an ether compound (i ii)
  • the photoelectric conversion element of the present invention using an electrolyte having excellent stability can continuously flow a DC current by light irradiation and efficiently transport ions.
  • the photoelectric conversion element of the present invention functions well as a solar cell.

Abstract

L'invention concerne des dispositifs de conversion photoélectrique fabriqués au moyen d'électrolytes contenant les constituants (A) et (B) suivants, et qui présentent une excellente stabilité à long terme : (A) est un composé éthéré représenté par les formules générales (I), (II), (III) ou (IV) dans lesquelles R?1 à R16 et R101 à R105¿ sont chacun hydrogène ou O(CH¿2?CH2O)a-A?1 (où A1¿ est alkyle ou alcényle ; et a est un nombre compris entre 1 et 12), à condition que dans chacune des formules (I) à (IV), R?1 à R16 et R101 à R105¿ ne soient pas tous simultanément hydrogène; et A est (CH¿2?)b-( b étant un nombre entier compris entre 1 et 12) ou O(CH2CH2O)c- (c étant un nombre compris entre 1 et 12)] ; et (B) est un couple redox composé d'iode et d'un composé iodé ou de brome et d'un composé bromé.
PCT/JP2000/001379 1999-03-10 2000-03-08 Dispositifs de conversion photoelectrique fabriques au moyen d'electrolytes etheres WO2000054361A1 (fr)

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Application Number Priority Date Filing Date Title
JP2000604485A JP4538955B2 (ja) 1999-03-10 2000-03-08 エーテル化合物の電解質を用いた光電変換素子

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JP6308099 1999-03-10
JP11/63080 1999-03-10

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010050575A1 (fr) 2008-10-29 2010-05-06 富士フイルム株式会社 Colorant, élément de conversion photoélectrique et cellule photoélectrochimique comprenant chacun le colorant, et procédé de fabrication du colorant
EP2302650A2 (fr) 2009-09-28 2011-03-30 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
EP2306479A2 (fr) 2009-09-28 2011-04-06 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
CN102471417A (zh) * 2009-07-15 2012-05-23 巴斯夫欧洲公司 共聚物、其作为增稠剂的用途及其制备方法
WO2012132855A1 (fr) 2011-03-30 2012-10-04 富士フイルム株式会社 Convertisseur photoélectrique et cellule photoélectrochimique
WO2014129575A1 (fr) 2013-02-22 2014-08-28 富士フイルム株式会社 Élément de conversion photoélectrique, procédé de fabrication d'élément de conversion photoélectrique et cellule solaire à colorant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084365A (en) * 1988-02-12 1992-01-28 Michael Gratzel Photo-electrochemical cell and process of making same
EP0720189A2 (fr) * 1994-12-29 1996-07-03 Ishihara Sangyo Kaisha, Ltd. Matériau composite (matériau poreux - électrolyte polymérique solide), méthode de fabrication et dispositif de conversion photoélectrique utilisant celui-ci
JPH09245848A (ja) * 1996-03-14 1997-09-19 Shin Etsu Chem Co Ltd 光充電式薄型電源素子
JPH09259943A (ja) * 1996-03-19 1997-10-03 Tokyo Gas Co Ltd 湿式太陽電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08236165A (ja) * 1994-12-29 1996-09-13 Ishihara Sangyo Kaisha Ltd 高分子固体電解質およびその製造方法ならびにそれを用いた光電変換素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084365A (en) * 1988-02-12 1992-01-28 Michael Gratzel Photo-electrochemical cell and process of making same
EP0720189A2 (fr) * 1994-12-29 1996-07-03 Ishihara Sangyo Kaisha, Ltd. Matériau composite (matériau poreux - électrolyte polymérique solide), méthode de fabrication et dispositif de conversion photoélectrique utilisant celui-ci
JPH09245848A (ja) * 1996-03-14 1997-09-19 Shin Etsu Chem Co Ltd 光充電式薄型電源素子
JPH09259943A (ja) * 1996-03-19 1997-10-03 Tokyo Gas Co Ltd 湿式太陽電池

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010050575A1 (fr) 2008-10-29 2010-05-06 富士フイルム株式会社 Colorant, élément de conversion photoélectrique et cellule photoélectrochimique comprenant chacun le colorant, et procédé de fabrication du colorant
EP2845882A2 (fr) 2008-10-29 2015-03-11 Fujifilm Corporation Colorant, élément de conversion photoélectrique et cellule photoélectrochimique
CN102471417A (zh) * 2009-07-15 2012-05-23 巴斯夫欧洲公司 共聚物、其作为增稠剂的用途及其制备方法
CN102471417B (zh) * 2009-07-15 2015-08-19 巴斯夫欧洲公司 共聚物、其作为增稠剂的用途及其制备方法
EP2302650A2 (fr) 2009-09-28 2011-03-30 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
EP2306479A2 (fr) 2009-09-28 2011-04-06 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
WO2012132855A1 (fr) 2011-03-30 2012-10-04 富士フイルム株式会社 Convertisseur photoélectrique et cellule photoélectrochimique
WO2014129575A1 (fr) 2013-02-22 2014-08-28 富士フイルム株式会社 Élément de conversion photoélectrique, procédé de fabrication d'élément de conversion photoélectrique et cellule solaire à colorant

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