EP2340547A1 - Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells - Google Patents

Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells

Info

Publication number
EP2340547A1
EP2340547A1 EP09783706A EP09783706A EP2340547A1 EP 2340547 A1 EP2340547 A1 EP 2340547A1 EP 09783706 A EP09783706 A EP 09783706A EP 09783706 A EP09783706 A EP 09783706A EP 2340547 A1 EP2340547 A1 EP 2340547A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
group
carotenoids
solar cells
following residues
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09783706A
Other languages
German (de)
French (fr)
Inventor
Hubert Hug
Claus Kilpert
Peter Mair
Wolfgang Schalch
Werner Simon
Adrian Wyss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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 DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to EP09783706A priority Critical patent/EP2340547A1/en
Publication of EP2340547A1 publication Critical patent/EP2340547A1/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/652—Cyanine dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a novel use of specific carotenoids; in particular it relates to the use of carotenoids as pigments in dye sensitized solar cells.
  • Dye-sensitized solar cells are a relatively new class of low-cost solar cells.
  • a well described example is the Graetzel cell.
  • a Graetzel cell is a photoelectrochemical system based on a semiconductor (e. g. TiO " 2 ) located between a photo-sensitized anode and an electrolyte (B. O'Regan & M. Graetzel, Nature 353, 737-740, 1991 ; Graetzel et al., United States Patent, No. 5,084,365, 1992; A. Hagefeldt & M. Graetzel, Ace. Chem. Res. 33, 269-277, 2000).
  • a semiconductor e. g. TiO " 2
  • Lutein and chlorophyll and a combination of both have recently also been shown to function as light harvesting pigments in a Graetzel cell (Liu Bao-Qi, Zhao Xiao-Peng. Acta Photonica Sinica, 35(2), 184-187, 2006).
  • the carotenoids according to the present invention are preferably chosen from one or more of the following groups 1 to 4.
  • n O, 1 , 2, 3 or 4;
  • n O or 1 ;
  • R is selected from the following residues: -NH-CH(RI )-COOR2, -0R3, -(Y) n -Z with
  • R1 H, or the residue of a protein-forming amino acid
  • Z -NH 2 , -OC(O)R4, -0R4, -COOR4; wherein R4 is selected from H, C- ⁇ - 6 -alkyl, -aryl or -heteroaryl, alkali or alkaline earth metal salts;
  • R3, R4 are independently from each other selected from H, a protected OH-group or an oxo-group;
  • R5 is the before mentioned residue the other R5 is a protected formyl group, e.g. a cyclic or acyclic acetal.
  • R1 , R2 are independently from each other selected from the following residues:
  • bixin and/or torularhodin More preferred are bixin and/or torularhodin; Most preferred is bixin.
  • Graphite was sprayed onto the cathode from a commercial lubricant product.
  • the electrodes were assembled with Teflon stripes of 1 mm width at the two borders without electric transfer contacts. The resistance between the contacts and the electrode were > 1 Ohm.
  • the solar cell was assembled, electrolyte solution was injected into the spaces of the electrodes and the solar cell was placed into the cell holder. Sun light was simulated with a 150 W Xenophot HLX lamp in 1 m distance. The temperature was controlled by a Peltron control unit.
  • the solar cells were connected to a labview-based device with which the voltage on the cell was regulated and the current was measured. The power was calculated from the IV curves.
  • Bixin showed the maximal light conversion efficiency ⁇ .

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Hybrid Cells (AREA)

Abstract

Use of specific carotenoids in dye sensitized solar cells. Preferred carotenoids according to the present invention are listed in the following : Bixin (A), Canthaxanthin (B), Astaxanthin (C), Zeaxanthin (D), Torularhodin (E).

Description

Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells
The present invention relates to a novel use of specific carotenoids; in particular it relates to the use of carotenoids as pigments in dye sensitized solar cells.
Dye-sensitized solar cells are a relatively new class of low-cost solar cells. A well described example is the Graetzel cell. A Graetzel cell is a photoelectrochemical system based on a semiconductor (e. g. TiO" 2) located between a photo-sensitized anode and an electrolyte (B. O'Regan & M. Graetzel, Nature 353, 737-740, 1991 ; Graetzel et al., United States Patent, No. 5,084,365, 1992; A. Hagefeldt & M. Graetzel, Ace. Chem. Res. 33, 269-277, 2000). A wide variety of organic dyes based on porphyrines and chlorophyll derivatives (A. Kay & M. Graetzel, J. Phys. Chem. 97, 6272-6277, 1993) and anthocyanins (NJ. Cherepy et al., J. Phsy. Chem. 101 , 9342- 9351 , 1997; A.S. Polo & N. Y. Murakami-lha, Solar Energy Material & Solar Cells 90, 1936-1944, 2006) have been used as light harvesting pigments.
Lutein and chlorophyll and a combination of both have recently also been shown to function as light harvesting pigments in a Graetzel cell (Liu Bao-Qi, Zhao Xiao-Peng. Acta Photonica Sinica, 35(2), 184-187, 2006).
But there is still a need for light harvesting pigments that may be used in dye sensitized solar cells. It was therefore an object of the present invention to provide ingredients having the desired properties as indicated above.
This objective has been solved by the carotenoids according to the present invention.
The carotenoids according to the present invention (one or more compounds) are preferably chosen from one or more of the following groups 1 to 4.
Group 1 : Asymmetric carotenoids of the structure
wherein
• A1, A2 are independently from each other selected from the following residues: -H, OH, =0, -OC(O)RI ;
• n = O, 1 , 2, 3 or 4;
• o = 1 or 2; and
• R is selected from the following residues:
with
R1 = hydrogen, C1-16-alkyl, C1-16-alkenyl or C5-8-cycloalkyl.
Group 2: Symmetric C30- and C40-carotenoids of the structure
wherein • A1, A2 are independently from each other selected from the following residues: -H, - OH, =0, -OC(O)R;
• B1 = H, B2 = H, OH, -OC(O)R or B1 and B2 together build =0;
• n = O or 1 ;
• R is selected from the following residues: -NH-CH(RI )-COOR2, -0R3, -(Y)n-Z with
R1 = H, or the residue of a protein-forming amino acid;
R2 = d-6-alkyl or C3-8-cycloalkyl;
R3 = Ci-16-alkyl or C3-8-cycloalkyl;
Y = d-7-alkylene or C2-7-alkenylene; n = O or 1
Z = -NH2, -OC(O)R4, -0R4, -COOR4; wherein R4 is selected from H, C-ι-6-alkyl, -aryl or -heteroaryl, alkali or alkaline earth metal salts;
Group 3: Hydroxy ketones with one of the structures I to
wherein
• m = 0, 1 , 2, 3 or 4
• n = 0 or 1 • p = 0, 1 or 2
• q = 0, 1 , 2 or 3
• r = 0, 1 or 2
• s = 1 or 2
• R is selected from H, alkyl, acyl; • R1 is Ci _ 6-alkyl; R2 = is C1 _ 6-alkyl or C2-6-alkenyl or R1 and R2 together build 1 ,4- tetramethylene or 1 ,5-pentamethylene;
• R3, R4 are independently from each other selected from H, a protected OH-group or an oxo-group; and
• either one or both R5 are o
,R1 "OH R2 , whereas in case only one R5 is the before mentioned residue the other R5 is a protected formyl group, e.g. a cyclic or acyclic acetal.
Group 4: Symmetric and asymmetric open chain carotenoids of the structure
wherein
• n = 0, 1 or 2; • m = 0 or 1 ;
• o = 0, 1 or 2; and
• R1 , R2 are independently from each other selected from the following residues:
-C(O)CH3, -CHO, -C(O)OR3, -C(O)CHO, with R3 = H, branched or linear Ci^o-alkyl. Preferred carotenoids according to the present invention are listed in the following:
Bixin
Canthaxanthin
Astaxanthin
Zeaxanthin
Torularhodin
More preferred are bixin and/or torularhodin; Most preferred is bixin.
The present invention is further illustrated by the following example, which is not intended to be limiting. Examples:
Example 1
Graetzel cells from ManSolar were set up in our laboratory in a standardized device. All carotenoids were dissolved in tetrahydrofuran (THF). THF contained butylated hydroxytoluene (BHT) to protect against peroxides. 10 mM stock solutions of carotenoids in THF/BHT were diluted. 200 μl of a 10 mM, 1 mM, and 0.1 mM carotenoid solution were directly pipetted onto the TiO2 layer of the anode and dried under an argon atmosphere. The electrodes (ITO glass) and the electrolyte were from ManSolar
(www.mansoiar.com). Graphite was sprayed onto the cathode from a commercial lubricant product. The electrodes were assembled with Teflon stripes of 1 mm width at the two borders without electric transfer contacts. The resistance between the contacts and the electrode were > 1 Ohm. The solar cell was assembled, electrolyte solution was injected into the spaces of the electrodes and the solar cell was placed into the cell holder. Sun light was simulated with a 150 W Xenophot HLX lamp in 1 m distance. The temperature was controlled by a Peltron control unit. The solar cells were connected to a labview-based device with which the voltage on the cell was regulated and the current was measured. The power was calculated from the IV curves.
The light conversion efficacy calculation (η) was performed in the following way: The surface area used in the solar station to measure the energy of simulated sun light was F = π r2 = π (0.45)2 cm2 = 0.64 cm2. The energy measured with UV filter was 70 mW / 0.64 cm2 = 110 mW / cm2. The TiO2 surface area of a solar cell (ManSolar) was 1.9 cm x 3 cm = 5.7 cm2. Therefore, the energy input was 110 mW / cm2 x 5.7 cm2 = 627 mW. The fill factor is a key parameter in evaluating the performance of solar cells. It is defined as the ratio of the actual maximum obtainable power (lmp x Vmp) to the theoretical power (lSc x VOc)- Lp and Vmp represent the current density and voltage at the maximum power point. This point is being obtained by varying the resistance in the circuit until I x V is at its greatest value.
Results
The following results were obtained by measuring carotenoids in THF the solar cells under defined conditions (Table 1 ): Table 1 :
Bixin showed the maximal light conversion efficiency η.
Figure 1 shows an efficiency (η) versus time plot of 10 mM Bixin in comparison to the solvent THF.

Claims

Claims:
1. Use of one or more compounds from the following groups 1 to 4 as pigments in dye sensitized solar cells:
Group 1 : Asymmetric carotenoids of the structure
wherein
• A1, A2 are independently from each other selected from the following residues: H1 -OH1 =O, -OC(O)RI ;
• n = 0, 1 , 2, 3 or 4;
• o = 1 or 2; and
• R is selected from the following residues:
with
R1 = hydrogen, Ci-i6-alkyl, Ci-i6-alkenyl or Cs-s-cycloalkyl.
Group 2: Symmetric C30- and C40-carotenoids of the structure
wherein
• A1, A2 are independently from each other selected from the following residues: H, -OH, =0, -OC(O)R;
• B1 = H, B2 = H, OH, -OC(O)R or B1 and B2 together build =0; • n = 0 or 1 ;
• R is selected from the following residues: -NH-CH(RI )-COOR2, -0R3, -(Y)n-Z with
R1 = H, or the residue of a protein-forming amino acid;
R2 = d-6-alkyl or C3-8-cycloalkyl; R3 = Ci-16-alkyl or C3-8-cycloalkyl;
Y = d-7-alkylene or C2-7-alkenylene; n = O or 1
Z = -NH2, -OC(O)R4, -0R4, -COOR4; wherein R4 is selected from H, C1-6-alkyl, -aryl or -heteroaryl, alkali or alkaline earth metal salts;
Group 3: Hydroxy ketones with one of the structures I to III:
wherein
• m = 0, 1 , 2, 3 or 4
• n = 0 or 1
• p = 0, 1 or 2
• q = 0, 1 , 2 or 3
• r = 0, 1 or 2
• s = 1 or 2
• R is selected from H, alkyl, acyl;
• R1 is Ci -6-alkyl; R2 = is Ci _6-alkyl or C2-6-alkenyl or R1 and R2 together build 1 ,4-tetramethylene or 1 ,5-pentamethylene;
• R3, R4 are independently from each other selected from H, a protected OH- group or an oxo-group; and
• either one or both R5 are
whereas in case only one R5 is the before mentioned residue the other R5 is a protected formyl group, e.g. a cyclic or acyclic acetal.
Group 4: Symmetric and asymmetric open chain carotenoids of the structure wherein
• n = 0, 1 or 2;
• m = 0 or 1 ;
• o = 0, 1 or 2; and
• R1 , R2 are independently from each other selected from the following residues:
-C(O)CH3, -CHO, -C(O)OR3, -C(O)CHO, with R3 = H, branched or linear Ci-2o-alkyl.
2. Use according to claim 1 wherein bixin and/or torularhodin are chosen as pigment(s).
3. Use according to claim 1 wherein the pigment is bixin.
4. Use according to one of the claims 1 to 3 wherein the (one or more) pigment(s) are used in combination with (one or more) chlorophyll(s).
EP09783706A 2008-10-03 2009-10-02 Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells Withdrawn EP2340547A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09783706A EP2340547A1 (en) 2008-10-03 2009-10-02 Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08165842 2008-10-03
PCT/EP2009/062848 WO2010037857A1 (en) 2008-10-03 2009-10-02 Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells
EP09783706A EP2340547A1 (en) 2008-10-03 2009-10-02 Novel use of specified carotenoids as light harvesting pigments in dye sensitized solar cells

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EP2340547A1 true EP2340547A1 (en) 2011-07-06

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Publication number Priority date Publication date Assignee Title
WO2014122315A1 (en) * 2013-02-11 2014-08-14 Dsm Ip Assets B.V. Increase of light conversion efficiency in dye-sensitized solar cells by natural photosensitizers and combination thereof
MX2021009165A (en) * 2019-01-30 2021-11-17 Tegula Solucoes Para Telhados Ltda Photovoltaic cell, method for manufacturing an encapsulated photovoltaic cell, electrical connection unit for a photovoltaic tile, and photovoltaic tile.
CN111430539A (en) * 2020-03-16 2020-07-17 电子科技大学 Long-life electronic skin and preparation method thereof
CN111430545A (en) * 2020-03-16 2020-07-17 电子科技大学 Organic solar cell based on astaxanthin additive and preparation method thereof
CN111430547B (en) * 2020-03-19 2023-10-17 电子科技大学 Organic solar cell based on astaxanthin cathode buffer layer and preparation method thereof

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JP3883120B2 (en) * 2002-03-29 2007-02-21 財団法人名古屋産業科学研究所 Porous zinc oxide thin film for dye-sensitized solar cell substrate, zinc oxide / dye composite thin film for photoelectrode material of dye-sensitized solar cell, production method thereof, and dye using zinc oxide / dye composite thin film as photoelectrode material Sensitized solar cell
WO2006130920A1 (en) * 2005-06-08 2006-12-14 Monash University Scattering elongate photovoltaic cell

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