Abstract
Semi-transparent photovoltaics only allow for the fabrication of solar cells with an optical transmission that is fixed during their manufacturing resulting in a trade-off between transparency and efficiency. For the integration of semi-transparent devices in buildings, ideally solar cells should generate electricity while offering the comfort for users to self-adjust their light transmission with the intensity of the daylight. Here we report photochromic dye-sensitized solar cells (DSSCs) based on dyes with a donor-π-conjugated-bridge-acceptor structure where the π-conjugated bridge is substituted by a diphenyl-naphthopyran photochromic unit. DSSCs show change in colour and self-adjustable light transmittance when irradiated and demonstrate a power conversion efficiency up to 4.17%. The colouration–decolouration process is reversible and these DSSCs are stable over 50 days. We also report semi-transparent photo-chromo-voltaic mini-modules (active area of 14 cm²) exhibiting a maximum power output of 32.5 mW after colouration.
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Next-generation applications for integrated perovskite solar cells
Communications Materials Open Access 05 January 2023
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Data availability
The datasets generated and analysed during the current study are available within the paper, its Supplementary Information and its Source Data files (cyclic voltammetry measurements, ultraviolet–visible characterizations, optical and electrical characterizations of solar cells (including: J(V) measurements, IPCE and AVT spectra), impedance spectroscopy measurements and I(V) measurements of the mini-module). All other data related to this work are available from the corresponding author upon reasonable request.
References
Hagfeldt, A., Boschloo, G., Sun, L., Kloo, L. & Pettersson, H. Dye-sensitized solar cells. Chem. Rev. 110, 6595–6663 (2010).
Mathew, S. et al. Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nat. Chem. 6, 242–247 (2014).
Kakiage, K. et al. Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes. Chem. Commun. 51, 15894–15897 (2015).
Yao, Z. et al. Dithienopicenocarbazole as the kernel module of low-energy-gap organic dyes for efficient conversion of sunlight to electricity. Energy Environ. Sci. 8, 3192–3197 (2015).
Green, M. A., Emery, K., Hishikawa, Y., Warta, W. & Dunlop, E. D. Solar cell efficiency tables (version 47). Prog. Photovolt. Res. Appl. 24, 3–11 (2016).
Cao, Y., Liu, Y., Zakeeruddin, S. M., Hagfeldt, A. & Grätzel, M. Direct contact of selective charge extraction layers enables high-efficiency molecular photovoltaics. Joule 2, 1108–1117 (2018).
Fakharuddin, A., Jose, R., Brown, T. M., Fabregat-Santiago, F. & Bisquert, J. A perspective on the production of dye-sensitized solar modules. Energy Environ. Sci. 7, 3952–3981 (2014).
Sauvage, F. A review on current status of stability and knowledge on liquid electrolyte-based dye-sensitized solar cells. Adv. Chem. 2014, 939525, 1–23 (2014).
Joly, D. et al. Metal-free organic sensitizers with narrow absorption in the visible for solar cells exceeding 10% efficiency. Energy Environ. Sci. 8, 2010–2018 (2015).
Yoon, S. et al. Application of transparent dye-sensitized solar cells to building integrated photovoltaic systems. Build. Environ. 46, 1899–1904 (2011).
Li, Y., Xu, G., Cui, C. & Li, Y. Flexible and semi-transparent organic solar cells. Adv. Energy Mater. 8, 1701791 (2018).
Eperon, G. E., Burlakov, V. M., Goriely, A. & Snaith, H. J. Neutral color semitransparent microstructured perovskite solar cells. ACS Nano 8, 591–598 (2014).
Della Gaspera, E. et al. Ultra-thin high efficiency semi-transparent perovskite solar cells. Nano Energy 13, 249–257 (2015).
Sun, J. & Jasieniak, J. J. Semi-transparent solar cells. J. Phys. D Appl. Phys. 50, 093001 (2017).
Brus, V. V. et al. Solution‐processed semi-transparent organic photovoltaics: from molecular design to device performance. Adv. Mater. 31, 1900904 (2019).
Guglielmetti, R. in Photochromism: Molecules and Systems (eds Durr, H. & Bouas-Laurent, H.) 314–466 (Elsevier, 2003).
Fihey, A., Perrier, A., Browne, W. R. & Jacquemin, D. Multiphotochromic molecular systems. Chem. Soc. Rev. 44, 3719–3759 (2015).
Wu, W. et al. A strategy to design novel structure photochromic sensitizers for dye-sensitized solar cells. Sci. Rep. 5, 8592 (2015).
Ma, S. et al. Smart photovoltaics based on dye-sensitized solar cells using photochromic spiropyran derivatives as photosensitizers. AIP Adv. 5, 057154 (2015).
Johnson, N.-M. et al. Photochromic dye-sensitized solar cells. AIMS Mater. Sci. 2, 503–509 (2015).
Tian, H., Boschloo, G. & Hagfeldt, A. Molecular Devices for Solar Energy Conversion and Storage. Green Chemistry and Sustainable Technology (Springer, 2018).
Ooyama, Y. & Harima, Y. Photophysical and electrochemical properties, and molecular structures of organic dyes for dye-sensitized solar cells. ChemPhysChem 13, 4032–4080 (2012).
Mishra, A., Fischer, M. K. R. & Bäuerle, P. Metal-free organic dyes for dye-sensitized solar cells: from structure:property relationships to design rules. Angew. Chem. Int. Ed. 48, 2474–2499 (2009).
Wang, P. et al. Stable and efficient organic dye-sensitized solar cell based on ionic liquid electrolyte. Joule 2, 2145–2153 (2018).
Minkin, V. I. Photo-, thermo-, solvato-, and electrochromic spiroheterocyclic compounds. Chem. Rev. 104, 2751–2776 (2004).
Tamasulo, M., Sortino, S., White, A. J. P. & Raymo, F. M. Fast and stable photochromic oxazines. J. Org. Chem. 70, 8180–8189 (2005).
Chu, N. Y. C. Photochromism: Molecules and Systems (eds Durr. H. & Bouas-Laurent, H.) (Elsevier, 2003).
Coelho, P. J., Salvador, M. A., Oliveira, M. M. & Carvalho, L. M. Synthesis of hydroxy-7H-benzo[c]fluoren-7-ones. Syn. Lett. 6, 1015–1018 (2004).
Van Gemert, B. Photochromic indeno-fused naphthopyrans. US patent 5645767 (1997).
Van Gemert, B., Crano, J. C. & Guglielmetti, R. Organic Photochromic and Thermochromic Compounds Vol. 1 111–140 (Kluwer Academic/Plenum Publishers, 1999).
Delbaere, S. & Vermeersch, G. NMR characterization of allenyl-naphthol in the photochromic process of 3,3-diphenyl-[3H]-naphtho[2-1,b]pyran. J. Photochem. Photobiol. A Chem. 159, 227–232 (2003).
Delbaere, S. et al. Kinetic and structural studies of the photochromic process of 3H-naphthopyrans by UV and NMR spectroscopy. J. Chem. Soc. Perkin Trans. 2, 1153–1158 (1998).
Demadrille, R., Rabourdin, A., Campredon, M. & Giusti, G. Spectroscopic characterisation and photodegradation studies of photochromic spiro[fluorene-9,3′-[3′H]-naphtho[2,1-b]pyrans]. J. Photochem. Photobiol. A Chem. 168, 143–152 (2004).
Hamann, T. W., Jensen, R. A., Martinson, A. B. F., Van Ryswyk, H. & Hupp, J. T. Advancing beyond current generation dye-sensitized solar cells. Energy Environ. Sci. 1, 66–78 (2008).
Ruhle, S. et al. Molecular adjustment of the electronic properties of nanoporous electrodes in dye-sensitized solar cells. J. Phys. Chem. B 109, 18907–18913 (2005).
Huaulmé, Q. et al. Functional panchromatic BODIPY dyes with near-infrared absorption: design, synthesis, characterization and use in dye-sensitized solar cells. Beilstein J. Org. Chem. 15, 1758–1768 (2019).
Huang, S. Y., Schlichthörl, G., Nozik, A. J., Grätzel, M. & Frank, A. J. Charge recombination in dye sensitized nanocrystalline TiO2 solar cells. J. Phys. Chem. B 101, 2576–2582 (1997).
Lee, Y. H. et al. Alkyl chain length dependence of the charge-transfer, recombination and electron diffusion length on the photovoltaic performance in double donor–acceptor-based organic dyes for dye sensitized solar cells. Dyes Pigments 133, 161–172 (2016).
Fabregat-Santiago, F., Garcia-Belmonte, G., Mora-Seró, I. & Bisquert, J. Characterization of nanostructured hybrid and organic solar cells by impedance spectroscopy. J. Phys. Chem. Chem. Phys. 13, 9083–9118 (2011).
Wang, Q. et al. Characteristics of high efficiency dye-sensitized solar cells. J. Phys. Chem. B 110, 25210–25221 (2006).
Wang, Q., Moser, J.-E. & Grätzel, M. Electrochemical impedance spectroscopic analysis of dye-sensitized solar cells. J. Phys. Chem. B 109, 14945–14953 (2005).
Idígoras, J., Pellejà, L., Palomares, E. & Anta, J.-A. The redox pair chemical environment influence on the recombination loss in dye-sensitized solar cells. J. Phys. Chem. C 118, 3878–3889 (2014).
Raga, S. R., Barea, E. M. & Fabregat-Santiago, F. Analysis of the origin of open circuit voltage in dye solar cells. J. Phys. Chem. Lett. 312, 1629–1634 (2012).
Chen, P. et al. High open-circuit voltage solid-state dye-sensitized solar cells with organic dye. Nano Lett. 9, 2487–2492 (2009).
Liu, B. et al. Photovoltaic performance of solid-state DSSCs sensitized with organic isophorone dyes: effect of dye-loaded amount and dipole moment. Dyes Pigments 94, 23–27 (2012).
Khenkin, M. V. et al. Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures. Nat. Energy 5, 35–49 (2020).
Zhang, Z., Ito, S., Moser, J.-E., Zakeeruddin, S. M. & Grätzel, M. Influence of iodide concentration on the efficiency and stability of dye-sensitized solar cell containing non-volatile electrolyte. ChemPhysChem 10, 1834–1838 (2009).
Te Velde, G. et al. Chemistry with ADF. J. Comput. Chem. 22, 931–967 (2001).
SCM Software for Chemistry and Materials: ADF (Vrije Universiteit, 2016); http://www.scm.com
Grimme, S., Anthony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Goerigk, J. & Grimme, S. A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions. Phys. Chem. Chem. Phys. 13, 6670–6688 (2011).
Shao, Y. H. et al. Advances in molecular quantum chemistry contained in the Q-Chem 4 program package. Mol. Phys. 115, 2315–2372 (2015).
Idígoras, J. et al. Organic dyes for the sensitization of nanostructured ZnO photoanodes: effect of the anchoring functions. RSC Adv. 5, 68929–68938 (2015).
Acknowledgements
R.D. acknowledges ANR for funding through the ODYCE project (grant agreement number ANR-14-OHRI-0003-01). J.L. acknowledges CEA for funding through a CFR PhD grant. P.M. thanks GENCI (CINES and IDRIS) for high-performance computing resources (grant 2019-A0060807648). J.A.A. and A.J.R. thank the Ministerio de Ciencia e Innovación of Spain and Agencia Estatal de Investigación and European Union (FEDER) under grant MAT2016-79866-R. A.J.R. thanks the Spanish Ministry of Education, Culture and Sports via a PhD grant (FPU2017-03684). V.M.M. thanks the French Embassy in Kenya through Campus France for a scholarship grant. R.D. acknowledges the European Research Council for funding. This project has received funding under the European Union’s Horizon 2020 research and innovation programme (grant agreement number 832606; project PISCO).
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Authors and Affiliations
Contributions
Q.H., D.J., J.L. and Y.K. synthesized and characterized the dyes. P.M. performed the DFT calculations. V.M.M., S.N. and F.O. fabricated, optimized and characterized the solar cells and mini-modules. A.J.R. and J.A.A. investigated the solar cells by EIS and performed the IPCE measurements. R.D. designed the materials and experiments. R.D. treated the data and wrote the manuscript, with contributions from all authors. All authors have given approval to the final version of the manuscript.
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Competing interests
R.D., D.J. and Y.K. are employees of CEA, which holds a patent on this technology (inventors: R.D., D.J. and Y.K.; current assignee: Commissariat à l’Energie Atomique et aux Energies Alternatives; application number: 17305597.1; date of publication: 28 November 2018). S.N is currently an employee of Solaronix, which sells electrodes and chemical components that are used in this study.
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Supplementary information
Supplementary Information
Supplementary Notes 1–8, Tables 1–14, Figs. 1–30 and refs. 1–6.
Supplementary Video
Demonstration of the simultaneous colouration and photovoltaic energy conversion for a photochromic semi-transparent solar cell (dimension of cell: 5 cm × 5 cm; indoor natural light).
Supplementary NMR Data
NMR spectra of the dyes and intermediates.
Supplementary Computational Data
Computational data for the three dyes.
Supplementary Figure Data
Source data for the: cyclic voltammetry traces (CV NPL, CV NPB and CV NPI); AVT of semi-transparent solar cells (AVT NPL, AVT NPB and AVT NPI); IPCE spectra of opaque solar cells (IPCE NPL, IPCE NPB and IPCE NPI); steady-state output, NPI-based opaque cell (SteadyState-NPI-Cell); and current–voltage characteristics of the NPI mini-module ((I(V) NPI-minimodule).
Source data
Source Data Fig. 2
Source data on ultraviolet–visible absorption spectra and kinetics (NPL, NPB and NPI).
Source Data Fig. 4
Source data on current–voltage characteristics for the solar cells (NPL, NPB and NPI).
Source Data Fig. 5
Source data on ultraviolet–visible absorption spectra, AVT, IPCE and bleaching curves for NPI-based semi-transparent solar cells.
Source Data Fig. 6
Source data on impedance spectroscopy measurements.
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Huaulmé, Q., Mwalukuku, V.M., Joly, D. et al. Photochromic dye-sensitized solar cells with light-driven adjustable optical transmission and power conversion efficiency. Nat Energy 5, 468–477 (2020). https://doi.org/10.1038/s41560-020-0624-7
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DOI: https://doi.org/10.1038/s41560-020-0624-7
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