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1.
Dye-sensitized solar cells (DSSCs) based on CuII/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open-circuit voltages (VOC, more than 1 V). However, their short-circuit photocurrent density (JSC) has remained modest. Increasing the JSC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO2 film and fast regeneration by the CuI complex. Herein, we report two new D-A-π-A-featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene-fused-quinoxaline (PFQ), respectively, as the auxiliary electron-withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 -based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near-quantitative collection of photogenerated charge carriers.  相似文献   

2.
A series of new push–pull organic dyes ( BT‐I – VI ), incorporating electron‐withdrawing bithiazole with a thiophene, furan, benzene, or cyano moiety, as π spacer have been synthesized, characterized, and used as the sensitizers for dye‐sensitized solar cells (DSSCs). In comparison with the model compound T1 , these dyes containing a thiophene moiety between triphenylamine and bithiazole display enhanced spectral responses in the red portion of the solar spectrum. Electrochemical measurement data indicate that the HOMO and LUMO energy levels can be tuned by introducing different π spacers between the bithiazole moiety and cyanoacrylic acid acceptor. The incorporation of bithiazole substituted with two hexyl groups is highly beneficial to prevent close π–π aggregation, thus favorably suppressing charge recombination and intermolecular interaction. The overall conversion efficiencies of DSSCs based on bithiazole dyes are in the range of 3.58 to 7.51 %, in which BT‐I ‐based DSSCs showed the best photovoltaic performance: a maximum monochromatic incident photon‐to‐current conversion efficiency (IPCE) of 81.1 %, a short‐circuit photocurrent density (Jsc) of 15.69 mA cm?2, an open‐circuit photovoltage (Voc) of 778 mV, and a fill factor (ff) of 0.61, which correspond to an overall conversion efficiency of 7.51 % under standard global AM 1.5 solar light conditions. Most importantly, long‐term stability of the BT‐I – III ‐based DSSCs with ionic‐liquid electrolytes under 1000 h of light soaking was demonstrated and BT‐II with a furan moiety exhibited better photovoltaic performance of up to 5.75 % power conversion efficiency.  相似文献   

3.
Subporphyrinatoboron(III) (SubB) sensitizers were synthesized for use in dye‐sensitized solar cells (DSSCs). The prototype, which comprises a sterically demanding 3,5‐di‐tert‐butylphenyl scaffold, a meso‐ethynylphenyl spacer, and a cyanoacrylic acid anchoring group, achieved an open‐circuit voltage VOC of 836 mV, short‐circuit current density JSC of 15.3 mA cm?2, fill factor of 0.786, and a photon‐to‐current conversion efficiency of 10.1 %. Such astonishing figures suggest that a bright future lies ahead for SubB in the realm of DSSCs.  相似文献   

4.
A series of porphyrin sensitizers that featured two electron‐donating groups and dual anchoring groups that were connected through a porphine π‐bridging unit have been synthesized and successfully applied in dye‐sensitized solar cells (DSSCs). The presence of electron‐donating groups had a significant influence on their spectroscopic, electrochemical, and photovoltaic properties. Overall, the dual anchoring groups gave tunable electronic properties and stronger attachment to TiO2. These new dyes were readily synthesized in a minimum number of steps in gram‐scale quantities. Optical and electrochemical data confirmed the advantages of these dyes for use as sensitizers in DSSCs. Porphyrins with electron‐donating amino moieties provided improved charge separation and better charge‐injection efficiencies for the studied dual‐push–pull dyes. Attenuated total reflectance–Fourier‐transform infrared (ATR‐FTIR) and X‐ray photoelectron spectroscopy of the porphyrin dyes on TiO2 suggest that both p‐carboxyphenyl groups are attached onto TiO2, thereby resulting in strong attachment. Among these dyes, cis-Zn2BC2A , with two electron‐donating 3,6‐ditertbutyl‐phenyl‐carbazole groups and dual‐anchoring p‐carboxyphenyl groups, showed the highest efficiency of 4.07 %, with JSC=9.81 mA cm?2, VOC=0.63 V, and FF=66 %. Our results also indicated a better photostability of the studied dual‐anchored sensitizers compared to their mono‐anchored analogues under identical conditions. These results provide insight into the developments of a new generation of high‐efficiency and thermally stable porphyrin sensitizers.  相似文献   

5.
Four organic D–A –π‐A‐featured sensitizers (TQ1, TQ2, IQ1, and IQ2) have been studied for high‐efficiency dye‐sensitized solar cells (DSSCs). We employed an indoline or a triphenylamine unit as the donor, cyanoacetic acid as the acceptor/anchor, and a thiophene moiety as the conjugation bridge. Additionally, an electron‐withdrawing quinoxaline unit was incorporated between the donor and the π‐conjugation unit. These sensitizers show an additional absorption band covering the broad visible range in solution. The contribution from the incorporated quinoxaline was investigated theoretically by using DFT and time‐dependent DFT. The incorporated low‐band‐gap quinoxaline unit as an auxiliary acceptor has several merits, such as decreasing the band gap, optimizing the energy levels, and realizing a facile structural modification on several positions in the quinoxaline unit. As demonstrated, the observed additional absorption band is favorable to the photon‐to‐electron conversion because it corresponds to the efficient electron transitions to the LUMO orbital. Electrochemical impedance spectroscopy (EIS) Bode plots reveal that the replacement of a methoxy group with an octyloxy group can increase the injection electron lifetime by a factor of 2.4. IQ2 and TQ2 can perform well without any co‐adsorbent, successfully suppress the charge recombination from TiO2 conduction band to I3? in the electrolyte, and enhance the electron lifetime, resulting in a decreased dark current and enhanced open circuit voltage (Voc) values. By using a liquid electrolyte, DSSCs based on dye IQ2 exhibited a broad incident photon‐to‐current conversion efficiency (IPCE) action spectrum and high efficiency (η=8.50 %) with a short circuit current density (Jsc) of 15.65 mA cm?2, a Voc value of 776 mV, a fill factor (FF) of 0.70 under AM 1.5 illumination (100 mW cm?2). Moreover, the overall efficiency remained at 97 % of the initial value after 1000 h of visible‐light soaking.  相似文献   

6.
Thieno[3,4‐c]pyrrole‐4,6‐dione‐based organic sensitizers with triphenylamine ( FNE38 and FNE40 ) or julolidine ( FNE39 and FNE41 ) as electron‐donating unit have been designed and synthesized. A linear hexyl group or a branched alkyl chain, the 2‐ethylhexyl group, is incorporated into molecular skeleton of the dyes to minimize intermolecular interactions. The absorption, electrochemical, and photovoltaic properties for these sensitizers were then systematically investigated. It is found that the sensitizers have similar photophysical and electrochemical properties, such as absorption spectra and energy levels, owing to their close chemical structures. However, the quasi‐solid‐state dye‐sensitized solar cells (DSSCs) based on the two types of sensitizers exhibit very different performance parameters. Upon the incorporation of the short ethyl group on the hexyl moiety, enhancements in both open‐circuit voltage (Voc) and short‐circuit current (Jsc) are achieved for the quasi‐solid‐state DSSCs. The Voc gains originating from the suppression of charge recombination were quantitatively investigated and are in good agreement with the experimentally observed Voc enhancements. Therefore, an enhanced solar energy conversion efficiency (η) of 6.16 %, constituting an increase by 23 %, is achieved under standard AM 1.5 sunlight without the use of coadsorbant agents for the quasi‐solid‐state DSSC based on sensitizer FNE40 , which bears the branched alkyl group, in comparison with that based on FNE38 carrying the linear alkyl group. This work presents a design concept for considering the crucial importance of the branched alkyl substituent in novel metal‐free organic sensitizers.  相似文献   

7.
The Y‐shaped, low molecular mass, hole‐conductor (HC), acidic coadsorbents 4‐{3,7‐bis[4‐(2‐ethylhexyloxy)phenyl]‐10H‐phenothiazin‐10‐yl}benzoic acid ( PTZ1 ) and 4‐{3,7‐bis[4‐(2‐ethylhexyloxy)phenyl]‐10H‐phenothiazin‐10‐yl}biphenyl‐4‐carboxylic acid ( PTZ2 ) were developed. Owing to their tuned and negative‐shifted HOMO levels (vs. NHE), they were used as HC coadsorbents in dye‐sensitized solar cells (DSSCs) to improve cell performance through desired cascade‐type hole‐transfer processes. Their detailed functions as HC coadsorbents in DSSCs were investigated to obtain evidence for the desired cascade‐type hole‐transfer processes. They have multiple functions, such as preventing π–π stacking of dye molecules, harvesting light of shorter wavelengths, and faster dye regeneration. By using PTZ2 as the tailor‐made HC coadsorbent on the TiO2 surface with the organic dye NKX2677, an extremely high conversion efficiency of 8.95 % was achieved under 100 mW cm?2 AM 1.5G simulated light (short‐circuit current JSC=16.56 mA cm?2, open‐circuit voltage VOC=740 mV, and fill factor of 73 %). Moreover, JSC was increased by 13 %, VOC by 27 % and power‐conversion efficiency by 49 % in comparison to an NKX2677‐based DSSC without an HC coadsorbent. This is due to the HC coadsorbent having a HOMO energy level well matched to that of the NKX‐2677 dye to induce the desired cascade‐type hole‐transfer processes, which are associated with a slower charge recombination, fast dye regeneration, effective screening of liquid electrolytes, and an induced negative shift of the quasi‐Fermi level of the electrode. Thus, this new class of Y‐shaped, low molecular weight, organic, HC coadsorbents based on phenothiazine carboxylic acid derivatives hold promise for highly efficient organic DSSCs.  相似文献   

8.
P(BDT‐TCNT) and P(DTBDAT‐TCNT) , which has an extended conjugation length, were designed and synthesized for applications in organic solar cell (OSCs). The solution absorption maxima of P(DTBDAT‐TCNT) with the extended conjugation were red‐shifted by 5–15 nm compared with those of P(BDT‐TCNT) . The optical band gaps and highest occupied molecular orbital (HOMO) energy levels of both P(BDT‐TCNT) and P(DTBDAT‐TCNT) were similar. The structure properties of thin films of these materials were characterized using grazing‐incidence wide‐angle X‐ray scattering and tapping‐mode atomic force microscopy, and charge carrier mobilities were characterized using the space‐charge limited current method. OSCs were formed using [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) as the electron acceptor and 3% diphenylether as additive suppress aggregation. OSCs with P(BDT‐TCNT) as the electron donor exhibited a power conversion efficiency (PCE) of 4.10% with a short‐circuit current density of JSC = 9.06 mA/cm2, an open‐circuit voltage of VOC = 0.77 V, and a fill factor of FF = 0.58. OSCs formed using P(DTBDAT‐TCNT) as the electron donor layer exhibited a PCE of 5.83% with JSC = 12.2 mA/cm2, VOC = 0.77 V, and FF = 0.62. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3182–3192  相似文献   

9.
In this work, high‐performance dye‐sensitized solar cells (DSSCs) based on new low‐cost visible nickel complex dye (VisDye), TiO2 nanoparticle/nanotube composites electrodes, carbon nanoparticles counter electrodes, and ionic liquids electrolytes have been fabricated. The electronic structure, optical spectroscopy, and electrochemical properties of the VisDye were studied. Experimental results indicate that it is beneficial to improve the electron transport and power conversion efficiency using the nickel complex VisDye and TiO2 nanoparticle/nanotube composites. Under optimized conditions, the solar energy conversion efficiencies were measured. The short‐circuit current density (JSC), the open‐circuit voltage (VOC), the fill factor (FF), and the overall efficiency (η) of the DSSCs are 10.01 mA/cm2, 516 mV, 0.68, and 3.52%, respectively. This study demonstrates that the combination of new VisDye with TiO2 nanoparticle/nanotube composites electrodes and carbon nanoparticles counter electrodes provide a way to fabricate highly efficient dye‐sensitized solar cells in low‐cost production.  相似文献   

10.
Three novel dyes of JJ1 , JJ2 , and JJ6 featured zinc porphyrin as a basic core structure; N, N‐alkyl‐4‐(prop‐1‐yn‐1‐yl)aniline as an electron donor linked to meso‐10‐position; 4‐(prop‐1‐yn‐1‐yl)benzoic acid as an electron acceptor linked to meso‐20‐position; and 2,6‐bis(dodecyloxy)phenyl or 2,6‐bis(octyloxy)phenyl respectively linked to meso‐5 and meso‐15‐positions of zinc porphyrin have been synthesized and used for dye‐sensitized solar cells. Porphyrin JJ6 featured the shortest alkyl group (─C4H9) on the donor, whereas JJ2 contained the longest alkyl groups (─C12H25), and JJ1 has a medium length of octyl groups. With these new porphyrin sensitizers, we observed that JJ6 has 7.55% power conversion efficiency under simulated one‐sun illumination (AM 1.5 G, 100 mW/cm2) with JSC = 18.64 mA/cm2, VOC = 0.66 V, and fill factor (FF) = 0.61, which was higher than the other two; JJ1 (7.35%) with JSC = 18.83 mA/cm2, VOC = 0.68 V, and FF = 0.60; and JJ2 (6.33%) with JSC = 15.69 mA/cm2, VOC = 0.62 V, and FF = 0.65. The power conversion efficiency of JJ6 and JJ1 were higher than JJ2 , demonstrating that the lengthy alkyl groups on the aniline cause a decrease in efficiency of the devices.  相似文献   

11.
Poly(n‐isopropylacrylamide) (PNIPAAm) and its nanocomposite with exfoliated montmorillonite (MMT) were prepared by soap‐free emulsion polymerization and individually applied to gel the electrolyte systems for the dye‐sensitized solar cells (DSSCs). Each exfoliated MMT nanoplatelet had a thickness of ~ 1 nm, carried ~ 1.8 cation/nm2, and acted like a two‐dimensional electrolyte. The DSSC with the LiI/I2/tertiary butylpyridine electrolyte system gelled by this polymer nanocomposite had higher short‐circuit current density (Jsc) compared to that gelled by the neat PNIPAAm. The former has a Jsc of 12.6 mA/cm2, an open circuit voltage (Voc) of 0.73 V, and a fill factor (FF) of 0.59, which harvested 5.4% electricity conversion efficiency (η) under AM 1.5 irradiation at 100 mW/cm2, whereas the latter has Jsc = 7.28 mA/cm2, Voc = 0.72 V, FF = 0.60, and η = 3.17%. IPCE of the nanocomposite‐gelled DSSC were also improved. Electrochemical impedance spectroscopy of the DSSCs revealed that the nanocomposite‐gelled electrolytes significantly decreased the impedances in three major electric current paths of DSSCs, that is, the resistance of electrolytes and electric contacts, impedance across the electrolytes/dye‐coated TiO2 interface, and Nernstian diffusion within the electrolytes. The results were also consistent with the increased molar conductivity of nanocomposite‐gelled electrolytes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 47–53, 2008  相似文献   

12.
We designed and synthesized a series of novel electron‐accepting zinc(II)phthalocyanines (ZnPc) and probed them in p‐type dye sensitized solar cells (p‐DSSCs) by using CuO as photocathodes. By realizing the right balance between interfacial charge separation and charge recombination, optimized fill factors (FFs) of 0.43 were obtained. With a control over fill factors in p‐DSSCs in hand we turned our attemtion to t‐DSSCs, in which we combined for the first time CuO‐based p‐DSSCs with TiO2‐based n‐DSSCs using ZnPc and N719. In the resulting t‐DSSCs, the VOC of 0.86 V is the sum of those found in p‐ and n‐DSSCs, while the FF remains around 0.63. It is only the smaller Jscs in t‐DSSCs that limits the efficiency to 0.69 %.  相似文献   

13.
An electrolyte based on the tris(acetylacetonato)iron(III)/(II) redox couple ([Fe(acac)3]0/1?) was developed for p‐type dye‐sensitized solar cells (DSSCs). Introduction of a NiO blocking layer on the working electrode and the use of chenodeoxycholic acid in the electrolyte enhanced device performance by improving the photocurrent. Devices containing [Fe(acac)3]0/1? and a perylene–thiophene–triphenylamine sensitizer (PMI–6T–TPA) have the highest reported short‐circuit current (JSC=7.65 mA cm?2), and energy conversion efficiency (2.51 %) for p‐type DSSCs coupled with a fill factor of 0.51 and an open‐circuit voltage VOC=645 mV. Measurement of the kinetics of dye regeneration by the redox mediator revealed that the process is diffusion limited as the dye‐regeneration rate constant (1.7×108 M ?1 s?1) is very close to the maximum theoretical rate constant of 3.3×108 M ?1 s?1. Consequently, a very high dye‐regeneration yield (>99 %) could be calculated for these devices.  相似文献   

14.
A series of simple phenothiazine‐based dyes, namely, TP , EP , TTP , ETP , and EEP have been developed, in which the thiophene (T), ethylenedioxythiophene (E), their dimers, and mixtures are present to modulate dye aggregation, charge recombination, and dye regeneration for highly efficient dye‐sensitized solar cell (DSSC) applications. Devices sensitized by the dyes TP and TTP display high power conversion efficiencies (PCEs) of 8.07 (Jsc=15.2 mA cm?2, Voc=0.783 V, fill factor (FF)=0.679) and 7.87 % (Jsc=16.1 mA cm?2, Voc=0.717 V, FF=0.681), respectively; these were measured under simulated AM 1.5 sunlight in conjunction with the I?/I3? redox couple. By replacing the T group with the E unit, EP ‐based DSSCs had a slightly lower PCE of 7.98 % with a higher short‐circuit photocurrent (Jsc) of 16.7 mA cm?2. The dye ETP , with a mixture of E and T, had an even lower PCE of 5.62 %. Specifically, the cell based on the dye EEP , with a dimer of E, had inferior Jsc and Voc values and corresponded to the lowest PCE of 2.24 %. The results indicate that the photovoltaic performance can be finely modulated through structural engineering of the dyes. The selection of T analogues as donors can not only modulate light absorption and energy levels, but also have an impact on dye aggregation and interfacial charge recombination of electrons at the interface of titania, electrolytes, and/or oxidized dye molecules; this was demonstrated through DFT calculations, electrochemical impedance analysis, and transient photovoltage studies.  相似文献   

15.
Panchromatic RuII sensitizers TF‐30–TF‐33 bearing a new class of 6‐quinolin‐8‐yl‐2,2′‐bipyridine anchor were synthesized and tested under AM1.5 G simulated solar irradiation. Their increased π conjugation relative to that of the traditional 2,2′:6′,2′′‐terpyridine‐based anchor led to a remarkable improvement in absorptivity across the whole UV–Vis–NIR spectral regime. Furthermore, the introduction of a bulky tert‐butyl substituent on the quinolinyl fragment not only led to an increase in the JSC value owing to the suppression of dye aggregation, but remarkably also resulted in no loss in VOC in comparison with the reference sensitizer containing a tricarboxyterpyridine anchor. The champion sensitizer in DSC devices was found to be TF‐32 with a performance of JSC=19.2 mA cm?2, VOC=740 mV, FF=0.72, and η=10.19 %. This 6‐quinolin‐8‐yl‐2,2′‐bipyridine anchor thus serves as a prototype for the next generation of RuII sensitizers with any tridentate ancillary.  相似文献   

16.
A series of new triarylamine‐based platinum‐acetylide complexes ( WY s) have been designed and synthesized as new sensitizers for applications in dye‐sensitized solar cells (DSSCs). With the aim of investigating the effect of a rigidifying donor structure on the photoelectrical parameters of the corresponding DSSCs, two new sensitizers, WY1 and WY2 , with rigid and coplanar fluorene units as an electron donor, were prepared. Moreover, two sensitizers that contained triphenylamine units as an electron donor, WY3 and WY4 , were also synthesized for comparison. The photo‐ and electrochemical properties of all of these new complexes have been extensively explored. We found that the dimethyl‐fluorene unit exhibited a stronger electron‐donating ability and better photovoltaic performance compared to the triphenylamine unit, owing to its rigidifying structure, which restricted the rotation of σ bonds, thus increasing the conjugation efficiency. Furthermore, WY2 , which contained a dimethyl‐fluorene unit as an electron donor and bithiophene as a π bridge, showed a relatively high open‐circuit voltage (Voc) of 640 mV and a PCE of 4.09 %. This work has not only expanded the choice of platinum‐acetylide sensitizers, but also demonstrates the advantages of restricted rotation of donor σ bonds for improved behavior of the corresponding DSSCs.  相似文献   

17.
A new donor‐acceptor copolymer, containing benzodithiophene (BDT) and methyl thiophene‐3‐carboxylate (3MT) units, is designed and synthesized for polymer solar cells (PSCs). The 3MT unit is used as an electron acceptor unit in this copolymer to provide a lower highest occupied molecular orbital (HOMO) level for obtaining polymer solar cells with a higher open‐circuit voltage (VOC). The resulting bulk heterojunction PSC made of the copolymer and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) exhibits a power conversion efficiency (PCE) up to 4.52%, a short circuit current (JSC) of 10.5 mA·cm‐2, and a VOC of 0.86 V.  相似文献   

18.
Three electron donor‐?? bridge‐electron acceptor (D‐π‐A) organic dyes bearing two carboxylic acid groups were applied to dye‐sensitized solar cells (DSSC) as sensitizers, in which one triphenylamine or modified triphenylamine and two rhodanine‐3‐acetic acid fragments act as D and A, respectively. It was found that the introduction of t‐butyl or methoxy group in the triphenylamine subunit could lead to more efficient photoinduced intramolecular charge transfer, thus improving the overall photoelectric conversion efficiency of the resultant DSSC. Under global AM 1.5 solar irradiation (73 mW·cm?2), the dye molecule based on methoxy‐substituted triphenylamine achieved the best photovoltaic performance: a short circuit photocurrent density (Jsc) of 12.63 mA·cm?2, an open circuit voltage (Voc) of 0.55 V, a fill factor (FF) of 0.62, corresponding to an overall efficiency (η) of 5.9%.  相似文献   

19.
A photoelectrochemical (PEC) cell consisting of an n‐type CdS single‐crystal electrode and a Pt counter electrode with the ruthenium–2,2′‐bipyridine complex [Ru(bpy)3]2+/3+ as the redox shuttle in a non‐aqueous electrolyte was studied to obtain a higher open‐circuit voltage (VOC) than the onset voltage for water splitting. A VOC of 1.48 V and a short‐circuit current (ISC) of 3.88 mA cm?2 were obtained under irradiation by a 300 W Xe lamp with 420–800 nm visible light. This relatively high voltage was presumably due to the difference between the Fermi level of photo‐irradiated n‐type CdS and the redox potential of the Ru complex at the Pt electrode. The smooth redox reaction of the Ru complex with one‐electron transfer was thought to have contributed to the high VOC and ISC. The obtained VOC was more than the onset voltage of water electrolysis for hydrogen and oxygen generation, suggesting prospects for application in water electrolysis.  相似文献   

20.
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