WO2013035207A1 - Contre-électrode de graphène pour cellule solaire à colorant - Google Patents

Contre-électrode de graphène pour cellule solaire à colorant Download PDF

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Publication number
WO2013035207A1
WO2013035207A1 PCT/JP2011/070671 JP2011070671W WO2013035207A1 WO 2013035207 A1 WO2013035207 A1 WO 2013035207A1 JP 2011070671 W JP2011070671 W JP 2011070671W WO 2013035207 A1 WO2013035207 A1 WO 2013035207A1
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WIPO (PCT)
Prior art keywords
counter electrode
dye
gnp
solar cell
sensitized solar
Prior art date
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PCT/JP2011/070671
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English (en)
Inventor
Ladislav Kavan
Jun-Ho Yum
Mohammad Khaja Nazeeruddin
Michael Graetzel
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Nec Corporation
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Priority to PCT/JP2011/070671 priority Critical patent/WO2013035207A1/fr
Publication of WO2013035207A1 publication Critical patent/WO2013035207A1/fr

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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
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • 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
    • 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
    • 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 counter electrode for a dye- sensitized solar cell and a dye-sensitized solar cell using the counter electrode.
  • the present invention also related to a method for manufacturing the counter electrode.
  • Dye sensitized solar cell also called Gratzel cell
  • DSC Dye sensitized solar cell
  • the generic device is a photoelectrochemical DSC, whose key components are dye-sensitized photoanode, electrolyte solution with a redox mediator and the cathode (counter electrode) material.
  • the cathode material is typically an optically transparent film of Pt
  • the quality of a catalytic electrode is characterized by a charge transfer resistance, R C T, which scales inversely with the exchange current density, y 0 :
  • Equation (1 ) provides an estimate of R C T of 1 .3 ⁇ 2 for the same yO value on the cathode. Such values are accessible for l 3 7l " on a Pt-FTO cathode as well as on thick (non-transparent) carbon layers.
  • Trancik et a/ stipulated that the carbonaceous film, which would, eventually, replace Pt-FTO for a cathode of DSC, should have the following parameters: at least 80% optical transparency at a wavelength of 550 nm, R C T of 2-3 ⁇ 2 and sheet resistance of 20 ⁇ /sq (Citation 5). Such a film was not yet demonstrated experimentally.
  • the redox potential of Co(lll)/Co(ll) can be tuned in the required range, that is between ca 0.4 to 0.7 V vs. SHE.
  • the corresponding DSCs exhibited an open-circuit voltage (V oc ) around 0.8 to 0.9 V which is significantly larger than that of the reference cell with ' /l " redox shuttle.
  • V oc open-circuit voltage
  • novel Co(lll)/(ll)-complex with tridentate pyridine-pyrazole ligand was introduced as a redox shuttle, rendering V oc over 1 V due to its higher redox potential.
  • Pt-FTO is not necessarily the optimal cathode for Co-mediated DSCs. That is, graphene nanoplatelets exhibit excellent activity in this device, outperforming Pt-FTO in many respects.
  • a counter electrode for a dye-sensitized solar cell including a cobalt complex- containing electrolyte solution, characterized in that the counter electrode includes a graphene sheet deposited on a transparent conductive substrate.
  • a dye-sensitized solar cell including a dye-sensitized photoanode, the above counter electrode facing to the photoanode with a gap, and an electrolyte solution comprising a cobalt complex in contact with both the photoanode and the counter electrode.
  • GNP Graphene nanoplatelets in the form of thin sem transparent film on F-doped SnO 2 (FTO) exhibit high electrocatalytic activity for Co(L) 2 ; where L is 6-(1H-pyrazol-1-yl)-2,2'-bipyridine.
  • This complex is one of the most promising redox mediators for a novel type of iodine-free dye-sensitized solar cell with open-circuit voltage exceeding 1 V.
  • Fig. 1A cyclic voltammograms of symmetrical dummy cells; scan rate 10 mV/s.
  • Fig. 1 B Optical absorbance at a wavelength of 550 nm plotted as a function of inverse charge transfer resistance determined from electrochemical impedance spectra.
  • Figs 1C and 1 D Nyquist plot of electrochemical impedance spectra measured from 65 kHz to 0.1 Hz on symmetrical dummy cells (bias 0 V). Lines are fitted curves to the equivalent circuit.
  • FIG. 4 Potential-step chronoamperometry on symmetrical dummy cell with the G84 electrodes. Potential step was from 0 V to 0.75 V, time 10 s.
  • FIG. 5 Current-voltage characteristics of dye sensitized solar cells.
  • Fig. 5A DSC with Pt-FTO counter electrode;
  • Fig. 5B DSC with GNP counter electrode (G66).
  • FIG. 7 Optical transmittance of GNP films. Inset shows the transmission at a wavelength of 550 nm (T 55 o) as a function of film's mass.
  • FIG. 9 Nyquist plot of electrochemical impedance spectra measured from 65 kHz to 0.1 Hz on symmetrical dummy cell with GNP electrodes (Fig. 9A) and Pt-FTO electrodes (Fig. 9B). Data points were fitted to the equivalent circuit shown in Fig. 2 (with Zw, pore omitted) and the fits are shown as full lines.
  • the fitted diffusion coefficients are: 3.2*10 "6 cm 2 /s (G85); 5.0*10 "6 cm 2 /s (G92); 3.4x10 '6 cm 2 /s (G95); 4.0x10 "6 cm 2 /s (Pt fresh (a) and Pt 13- days old (b)).
  • Fig. 9C Cyclic voltammogram on a symmetrical dummy cell with Pt-FTO electrodes (13 days old); scan rate 10 mV/s.
  • Interfacial charge transfer and mass transport in acetonitrile solution of Co(L)2 were characterized by using cyclic voltammetry, potential-step chronoamperometry and electrochemical impedance spectroscopy on symmetrical thin-layer dummy cells.
  • the exchange current density for the Co 2+/3+ (L)2 redox reaction scaled linearly with the optical absorbance of GNP films.
  • the exchange currents for Co 2+ 3+ (L) 2 couple on GNP- electrode are larger by a factor of about 25 or 160 than those for the l 3 7l " couple on the same electrode (depending on the reference electrolyte used).
  • Dye-sensitized solar cells with Y123+TiO 2 photoanode demonstrate impressive energy conversion efficiencies between 8 to 10 % for both GNP and Pt-based cathodes.
  • the cell with GNP cathode is outperforming that with Pt-FTO particularly in fill factors and in the efficiency at higher illumination intensities. This is an obvious effect of smaller RCT at the GNP cathode, but there is also a slight increase of dark current for GNP-based device, which reduces efficiency at 0.1 sun and the V oc . ⁇ 0017 ⁇
  • Graphene nanoplatelets Grade 3 (GNP) purchased from Cheap Tubes, Inc. (USA) are used as a graphene sheet.
  • the GNP has a flake shape.
  • the GNP consists of several sheets of graphene with an overall thickness of approximately 5 nanometers (ranging from 1 nm to 15 nm) and particle diameters less than 2 microns, surface area of 600 - 750 m 2 /g.
  • the platelets were dispersed in 2- propanol by sonication (ca. 1 minute) and the dispersion was left overnight to separate big particles by sedimentation.
  • the supernatant dispersion containing about 1.2 mg/mL of the GNP was stable for several days without further marked sedimentation.
  • FTO glass (TEC 15 from Libbey-Owens-Ford, 15 Ohm/sq) was ultrasonically cleaned in isopropanol followed by 30 min treatment in UVO-Cleaner (model 256-220, Jelight Co., Inc.). The stock GNP dispersion, which was sometimes diluted to concentrations between 0.6 mg/L and 0.3 mg/mL, was then drop-casted on the cleaned FTO. A uniform semitransparent film was obtained after drying at room temperature. The amount of deposited graphene was adjusted by concentration of the used dispersion and/or by repeating the drop cast deposition. The film was finally annealed in Ar atmosphere at 500°C for 1 hour. Platinized FTO was prepared by deposition of ca. 5 L/cm 2 of 10 mM hfePtCle in 2-propanol and calcination at 400°C for 15 minutes.
  • the symmetrical sandwich dummy cell was fabricated from two identical FTO sheets which were separated by 70 ⁇ thick Surlyn (R) tape ⁇
  • the electrolyte solution contained 0.22 M of Co(L)2(PFe)2, 0.05 M of Co(L) 2 (PF 6 ) 3 , 0.1 M of LiCIO 4 , and 0.2 M of 4-ferf-butylpyridine in acetonitrile; where L being 6-(1 H-pyrazol-1-yl)-2,2'-bipyridine.
  • Co(L)2(PF6)2 is represented by the following formula:
  • R H or CH j ⁇ 0027 ⁇
  • Photoelectrochemical tests were carried out with a ⁇ 2 electrode manufactured by a 'double layer' architecture: a transparent layer (thickness 4.5 pm) composed of nanocrystalline anatase having « 20 nm particle size, which was deposited on the surface of a TiCU-treated FTO, and a scattering layer (thickness 4.2 pm) made from 400 nm sized particles (CCIC, HPW-400), and the final film was again treated with TiCI 4 .
  • the T1O2 electrode was sensitized with 3[6-[4-[bis(2',4'-dihexyloxybiphenyl-4-yl)amino-]phenyl]-4,4- dihexyl-cyclopenta-[2,1-b:3,4-b']dithiophene-2-yl]-2-cyanoacrylic acid, coded Y123, by overnight dipping.
  • the T1O2 electrode was assembled with a counter electrode using a Surlyn (R) tape (25 pm in thickness) as a sealant and a spacer (see above).
  • the cell active area for illumination was 0.2 cm 2 , defined by a mask.
  • Electrochemical measurements were carried out using a potentiostat (PAR 273, EG&G) interfaced to a frequency response analyzer of Solatron 1260A and controlled by CorrWare program. Electrochemical impedance data were processed using Zplot Zview software. The impedance spectra were acquired in the frequency range from 65 kHz to 0.1 Hz, at 0 V bias voltage, the modulation amplitude was 10 mV. The optical spectra were measured by Varian Cary 5 spectrometer with integrating sphere in transmission mode. Blank FTO sheet served as a reference. For
  • the light source was a 450 W xenon light source (Osram XBO 450, Germany) with a filter (Schott 113).
  • the light power was regulated to the AM 1.5G solar standard by using a reference Si photodiode equipped with a color-matched filter (KG-3, Schott) to reduce the mismatch in the region of 350-750 nm between the simulated light and AM 1.5G to less than 4%.
  • the differing intensities were regulated with neutral wire mesh attenuator.
  • the applied potential and cell current were measured using a digital source meter (Keithley model 2400).
  • the used redox shuttle was Co 2+ 3+ (L) 2 ; where L is 6-(1H-pyrazol-1-yl)-2,2'-bipyridine (see the formula in Fig. 6) in acetonitrile medium. It is a particularly promising redox mediator, because it allows achieving open-circuit voltage larger than 1 V in dye-sensitized solar cell.
  • Fig. 1 presents electrochemical behavior of symmetrical dummy cells with this electrolyte solution and two identical GNP electrodes having various amounts of graphene nanoplatelets deposited on FTO.
  • the GNP loading is labeled arbitrarily as the corresponding optical transmission of the active layer measured at the wavelength of 550 nm, T550.
  • Fig. 1 A presents cyclic voltammograms of dummy cells with GNP electrodes and also with pure FTO for comparison. The latter material shows almost no electrochemical activity at these conditions.
  • Electrocatalytic activity of GNP films is more accurately characterized by electrochemical impedance spectra shown in Figs. 1 C and 1 D.
  • the experimental data can be fitted to the equivalent circuit shown in Fig. 2, where Rs is the ohmic serial resistance, Zw.pore is the Nernst diffusion impedance in the pores of carbonaceous material, Zw is the Nernst diffusion impedance in the bulk electrolyte between electrodes and CPE is constant phase element describing deviation from the ideal capacitance, due to the roughness of the electrodes.
  • the corresponding impedance of a constant phase element, ZQPE equals:
  • the parameter Zw.pore was introduced by Roy- Mayhew et al. (Citation 3) for electrodes made from functionalized graphene sheets in contact with " / ⁇ electrolyte solution. This additional impedance manifests itself as a third semicircle, which shows up in the high-frequency region of the spectrum measured at applied bias.
  • the parameter Zw.pore can be omitted for Pt-FTO where the catalytic reaction occurs on virtually non-porous surface. (see, Citations 3 and 4) Also in the present case, the diffusion in pores can, obviously, be neglected, because the amount of GNP is too small to create a porous layer on top of FTO.
  • the CPE parameter, S is roughly proportional to RCT which evidences that the electrocatalytic activity is related to the surface area of graphene nanoplatelets. This further manifests itself as a linear fit between the optical absorbance of GNP electrodes (-logr 550 ) and the inverse charge transfer resistance, 1//3 ⁇ 4 ⁇ as in the case of GNP
  • Fig. 3 shows the impedance plots for a freshly assembled cell with the G84 electrodes and those after 2 to 11 days of aging. A similar aging effect was ascribed to 'poisoning' of platinum. (Citation 4) However, the aging of GNP in contact to Co(lll)/(ll) redox electrolyte is slower at comparable conditions. Cyclic voltammograms of G84 dummy cell (data not shown) exhibited no marked aging-dependent changes of their shapes, and also the limiting currents were identical within the experimental errors.
  • the current follows the semi-infinite Cottrell-like decay.
  • the current drops linearly with f 1 2 (f is time) as long as the concentration profiles in front of each electrode merge to form a single linear profile.
  • the current attains a constant value, similar to the limiting current observed in cyclic voltammograms, about 8.5 mA/cm 2 (cf. Fig. 1A).
  • Extrapolation of both linear components of the chronoamperometric plot provides intersection at the so- called transition time, ⁇ which defines the diffusion coefficient, D: ⁇ 0044 ⁇
  • Table 2 Characteristics of solar cells with Y123-sensitized TiO 2 photoanode and Pt or GNP (G66) cathode under various light intensities (/ 0 ).

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

L'invention porte sur une contre-électrode pour cellule solaire à colorant ayant une solution d'électrolyte à teneur en complexe du cobalt, qui comprend une feuille de graphène, en particulier des nanoplaquettes de graphène, sur un substrat conducteur transparent.
PCT/JP2011/070671 2011-09-05 2011-09-05 Contre-électrode de graphène pour cellule solaire à colorant WO2013035207A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006202721A (ja) * 2004-12-22 2006-08-03 Fujikura Ltd 光電変換素子用の対極及び光電変換素子
JP2006318770A (ja) * 2005-05-13 2006-11-24 Japan Carlit Co Ltd:The 色素増感型太陽電池の触媒電極、及びそれを備えた色素増感型太陽電池
JP2007317446A (ja) * 2006-05-24 2007-12-06 Dai Ichi Kogyo Seiyaku Co Ltd 色素増感太陽電池
JP2008066018A (ja) * 2006-09-05 2008-03-21 Fujikura Ltd 対極及びその製造方法、並びに光電変換素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006202721A (ja) * 2004-12-22 2006-08-03 Fujikura Ltd 光電変換素子用の対極及び光電変換素子
JP2006318770A (ja) * 2005-05-13 2006-11-24 Japan Carlit Co Ltd:The 色素増感型太陽電池の触媒電極、及びそれを備えた色素増感型太陽電池
JP2007317446A (ja) * 2006-05-24 2007-12-06 Dai Ichi Kogyo Seiyaku Co Ltd 色素増感太陽電池
JP2008066018A (ja) * 2006-09-05 2008-03-21 Fujikura Ltd 対極及びその製造方法、並びに光電変換素子

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