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. 2024 Jul 20;6(15):8939-8949.
doi: 10.1021/acsapm.4c01238. eCollection 2024 Aug 9.

Improved Interfacial Electron Dynamics with Block Poly(4-vinylpyridine)-Poly(styrene) Polymers for Efficient and Long-Lasting Dye-Sensitized Solar Cells

Daniela F S L Rodrigues  1   2 , Carlos M R Abreu  1 , Frédéric Sauvage  3 , Jorge F J Coelho  1   4 , Arménio C Serra  1 , Dzmitry Ivanou  2   5 , Adélio Mendes  2   5
Affiliations

Improved Interfacial Electron Dynamics with Block Poly(4-vinylpyridine)-Poly(styrene) Polymers for Efficient and Long-Lasting Dye-Sensitized Solar Cells

Daniela F S L Rodrigues et al. ACS Appl Polym Mater. .

Abstract

Dye-sensitized solar cells (DSSCs) have recently entered the market for indoor photovoltaics. Fast electron injection from dye to titania, the lifetime of the excited dye, and the suppression of back electron recombination at the photoanode/electrolyte interface are crucial for a high photocurrent conversion efficiency (PCE). This study presents block copolymers of poly(4-vinylpyridine) and poly(styrene)-P4VP67-b-PSt x (x=23;61) as efficient accelerators of electron injection from dye to titania with extended lifetime excited states and long-lasting back electron recombination suppression. P4VP67-b-PSt23 and P4VP67-b-PSt61 rendered devices with PCEs of 10.0 and 9.8%, respectively, under AM 1.5G light; PCEs of 19.4 and 16.4% under 1000 lx LED light were attained. Copolymers provided a stable PCE with the two most popular I3 -/3I- electrolytes based on ACN and 3-methoxypropionitrile solvents; PCE history was tracked in the dark and under 1000 h of continuous light soaking with passive load according to ISOS-D1 and ISOS-L2 aging protocols, respectively. The impact of the polymer molecular structure on electron recombination, charge injection, dye anchoring, light absorption, photocurrent generation, and PCE and the long-term history of photovoltaic metrics are discussed.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Molecular structure of P4VP67-b-PStx (x=23;61) block copolymers.
Figure 2
Figure 2
I–V curves of DSSCs produced with the pristine TiO2/N719 photoanode and with adsorbed P4VP or P4VP67-b-PStx polymers: photocurrent under AM 1.5G (100 mW cm–2) (a) without and (b) with the aperture mask. (c) Plot showing the current density in the dark.
Figure 3
Figure 3
I–V curves of DSSCs with photoanodes passivated with P4VP67-b-PStx copolymers and the P4VP homopolymer obtained under different intensities of LED illumination.
Figure 4
Figure 4
IPCE spectra of DSSCs recorded (a) without and (b) with the aperture mask.
Figure 5
Figure 5
(a) Impedance response of DSSCs with the pristine TiO2/N719 photoanode and after coadsorption of polymers. (b) Equivalent electrical circuit used to fit the spectra. Solid lines show fittings to the equivalent circuit. Spectra were recorded in the dark at a potential 20 mV below the VOC.
Figure 6
Figure 6
Normalized absorption spectra of the pristine TiO2/N719 layer and after coadsorption of the polymers.
Figure 7
Figure 7
Simplified energy-kinetic diagram for electron injection from N719 to titania. The energy levels are presented with respect to the normal hydrogen electrode; plotted with the use of data of refs (48,49) and TCSPC data obtained in this study.
Figure 8
Figure 8
Time-resolved photoluminescence decay between devices with the pristine photoanode and with coadsorbed polymers. Bold lines stand for the fit results using a biexponential function. The instrument response function (IRF) is plotted with “star” symbols.
Figure 9
Figure 9
History of photovoltaic metrics (no aperture mask) of DSSCs with EL-HPE and EL-HSE electrolytes within ISOS-D1 (a gray area in the plot) and ISOS-L2 (a light area in the plot) testing protocols: (a, e) PCE; (b, f) JSC; (c, g) VOC; and (d, h) FF.
Figure 10
Figure 10
FTIR spectra of (1) pristine anatase nanoparticles and after immersing in an ethanol solution of (2) P4VP, (3) P4VP67-b-PSt23, and (4) P4VP67-b-PSt61.
See this image and copyright information in PMC

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