ABSTRACT
The ternary strategy has been recognized as an effective method to improve the photovoltaic performance of organic solar cells (OSCs). In ternary OSCs, the complementary or broadened absorption spectrum, optimized morphology, and enhanced photovoltaic performance could be obtained by selecting a third rational component for the host system. In this work, a fused ring electron acceptor named BTMe-C8-2F, which possesses a high-lying lowest unoccupied molecular orbital (LUMO) energy level and a complementary absorption spectrum to PM6:Y6, was introduced to a PM6:Y6 binary system. The ternary blend film PM6:Y6:BTMe-C8-2F showed high and more balanced charge mobilities, and low charge recombination. Therefore, the OSC based on the PM6:Y6:BTMe-C8-2F (1 : 1.2 : 0.3, w/w/w) blend film achieved the highest power conversion efficiency (PCE) of 17.68%, with an open-circuit voltage (VOC) of 0.87 V, a short-circuit current (JSC) of 27.32 mA cm-2, and a fill factor (FF) of 74.05%, which are much higher than the binary devices of PM6:Y6 (PCE = 15.86%) and PM6:BTMe-C8-2F (PCE = 11.98%). This work provides more insight into the role of introducing a fused ring electron acceptor with a high-lying LUMO energy level and complementary spectrum for simultaneously enhancing the VOC and JSC to promote the performance of ternary OSCs.
ABSTRACT
The small molecule 5,15-di(thiophen-2-yl) porphyrin (TP) was developed for new dual-ion symmetric organic batteries (DSOBs). It delivered a capacity of 150 mA h g-1 at 0.2 A g-1 with a high voltage of 2.7 V, and up to 1500 cycles were achieved. This work offers a new approach for developing high-performance dual-ion organic symmetric batteries.
ABSTRACT
Organic cathode materials have recently attracted abundant attention due to their flexible structural tunability and recyclability. However, the low intrinsic electrical conductivity and high solubility in electrolytes of organic electrode materials have significantly limited their practical application. Herein, we present [5,15-bis(ethynyl)-10,20-difurylporphinato] copper(II) (CuDEOP) as a new cathode for rechargeable organic lithium batteries (ROLBs). The combination of both ethynyl and furyl groups of the CuDEOP cathode with a nanorod structure renders it with enhanced structural stability and an extended delocalized π-electron system to deliver excellent cycling stability (capacity retention of 76% after 6000 cycles) and a high power density (16 kW kg-1). The furyl electroactive groups participate in charge storage contribution to achieve a reversible six-electron-transfer redox reaction in a specific voltage range. The mechanism characterizations indicate that the nitrogen atoms on the porphyrin ring act as active sites to alternatively store both PF6- anions and Li+ cations, and the charge storage process is a pseudocapacitive-dominated reaction. This observation will offer a new avenue for designing functionalized molecules for electrochemical energy-storage (EES) systems.
ABSTRACT
To face the challenge of all-climate application, organic rechargeable batteries must hold the capability of efficiently operating both at high temperatures (>50 °C) and low temperatures (-20 °C). However, the low electronic conductivity and high solubility of organic molecules significantly impede the development in electrochemical energy storage. This issue can be effectively diminished using functionalized porphyrin complex-based organic cathodes by the in-situ electropolymerization of electrodes at elevating temperatures during electrochemical cycling. [5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP)- and 5,15-bis(ethynyl)-10,20-diphenylporphinato (DEPP)-based cathodes are proposed as models, and it is proved that a largely improved electrochemical performance is observed in both cathodes at a high operating temperature. Reversible capacities of 249 and 105 mA h g-1 are obtained for the CuDEPP and DEPP cathodes after 1000 cycles at 50 °C, respectively. The result indicates that the temperature-induced in situ electropolymerization strategy responds to the enhanced electrochemical performance. This study would open new opportunities for developing highly stable organic cathodes for electrochemical energy storage even at high temperatures.
ABSTRACT
In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π-π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π-π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π-π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance.
ABSTRACT
The energy offset, considered as the driving force for charge transfer between organic molecules, has significant effects on both charge separation and charge recombination in organic solar cells. Herein, we designed material systems with gradually shifting energy offsets, including both positive and negative values. Time-resolved spectroscopy was used to monitor the charge dynamics within the bulk heterojunction. It is striking to find that there is still charge transfer and charge generation when the energy offset reached -0.10 eV (ultraviolet photoelectron spectroscopy data). This work not only indicates the feasibility of the free carrier generation and the following charge separation under the condition of a negative offset but also elucidates the relationship between the charge transfer and the energy offset in the case of polymer chlorination.
ABSTRACT
Three cationic polyelectrolytes polyethyleneimine ethoxylate (PEIE)-1,4-butanediol dimethylsulfonate (MSB), PEIE-1,4-butanediol diethylsulfonate (ESB), and PEIE-1,4-butanediol dibenzylsulfonate (BSB), containing methylsulfonate, ethylsulfonate, and benzylsulfonate, respectively, were prepared for cathode interface layers (CILs) via a one-step reaction with 1,4-butanediol dialkylsulfonate and PEIE as the reactants. The results indicate that PEIE-MSB and PEIE-ESB with smaller counterions possess more efficient electron extraction, higher electron mobilities, and better photovoltaic performance than PEIE-BSB with larger counterions. The PTB7-Th:PC71BM-based single junction bulk heterojunction polymer solar cells (PSCs) with PEIE-ESB as the CIL showed power conversion efficiencies (PCEs) of 10.44 and 9.23% under the thickness conditions of 8 and 30 nm, respectively. The PM6:Y6-based PSCs displayed a high PCE of 15.69%. The study provides not only new high-performance CILs but also a new strategy to construct light-soaking-free PSCs via tuning alkylsulfonate counterions.
ABSTRACT
Morphology control in laboratory and industry setting remains as a major challenge for organic solar cells (OSCs) due to the difference in film-drying kinetics between spin coating and the printing process. A two-step sequential deposition method is developed to control the active layer morphology. A conjugated polymer that self-assembles into a well-defined fibril structure is used as the first layer, and then a non-fullerene acceptor is introduced into the fibril mesh as the second layer to form an optimal morphology. A benefit of the combined fibril network morphology and non-fullerene acceptor properties was that a high efficiency of 16.5% (certified as 16.1%) was achieved. The preformed fibril network layer and the sequentially deposited non-fullerene acceptor form a robust morphology that is insensitive to the polymer batches, solving a notorious issue in OSCs. Such progress demonstrates that the utilization of polymer fibril networks in a sequential deposition process is a promising approach towards the fabrication of high-efficiency OSCs.
ABSTRACT
A highly conjugated polymeric porphyrin with an ethynyl group is proposed as a new cathode for lithium organic batteries. The electrochemical performance is significantly improved after a simple coupled polymerization, resulting in excellent cycling stability with a capacity retention of 99.2% for 2000 cycles.
ABSTRACT
Rechargeable potassium-ion batteries (KIBs) are promising alternatives to lithium-ion batteries for large-scale electrochemical energy-storage applications because of the abundance and low cost of potassium. However, the development of KIBs is hampered by the lack of stable and high-capacity cathode materials. Herein, a functionalized porphyrin complex, [5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP), was proposed as a new cathode for rechargeable potassium batteries. Spectroscopy and molecular simulation studies were used to show that both PF6 - and K+ interact with the porphyrin macrocycle to allow a four-electron transfer. In addition, the electrochemical polymerization of the ethynyl functional groups in CuDEPP resulted in the self-stabilization of the cathode, which was highly stable during cycling. This unique charge storage mechanism enabled CuDEPP to provide a capacity of 181â mAh g-1 with an average potential of 2.8â V (vs. K+ /K). These findings could open a pathway towards the design of new stable organic electrodes for KIBs.
ABSTRACT
In this contribution, a series of A-π-D-π-A small molecules (SMs), IPY-T-IC, IPY-T-ICCl, and IPY-T-ICF, containing the central donor unit (D) of 6,12-dihydro-diindolo[1,2-b:10,20-e]pyrazine (IPY), the π-conjugated bridge of thiophene, and the end-accepting group (A) of 3-(dic yanomethylidene)indol-1-one, 5,6-dichloro-3-(dicyanomethylidene)indol-1-one, or 5,6-difluoro-3-(dicyanomethylene)indol-1-one, were developed, characterized, and employed as the acceptor materials for polymer solar cells (PSCs). Influences of the different end-accepting groups on thermal properties, spectral absorption, energy levels, photovoltaic performance, and film morphology of these small-molecule acceptors (SMAs) were investigated in detail. These SMAs exhibit an excellent thermal stability and strong crystallization. The absorption spectra of these SMs mainly locate the wavelength between 400 and 700 nm, associated with the optical band gaps in the range of 1.75-1.90 eV. Compared with nonhalogenated IPY-T-IC, the halogenated SMAs IPY-T-ICCl and IPY-T-ICF present better absorption abilities, wider absorption region, and downshifted highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels. With regard to the complementary spectral absorption and matched HOMO/LUMO levels, PTB7-Th as a low-band gap polymer was chosen to be an electron donor to pair with these SMAs for fabricating bulk-heterojuntion PSCs. Under optimized conditions, among these SMAs, the PTB7-Th:IPY-T-IC-based PSC processed from a halogenated solvent system (chlorobenzene + 1-chloronaphthalene) delivers the best power conversion efficiency (PCE) of 7.32%, mainly because of more complementary spectral absorption, upper-lying LUMO level, higher and balanced carrier mobility, more efficiently suppressed trap-assisted recombination, better charge collection property, and blend morphology. Encouragingly, an improved PCE of up to 7.68% is achieved when the IPY-T-IC-based solar cell was processed from a nonhalogenated solvent system (o-xylene + 2-methylnaphthalene). In view of the large band gap of these IPY-based SMAs, the PCE of over 7.5% is notable and attractive for the related community. Our study argues that the IPY moiety is a potential electron-donating building moiety to develop medium-band-gap high-performance A-π-D-π-A SMAs for nonhalogenated-solvent-processed photovoltaic devices.
ABSTRACT
A novel small-molecule (SM) acceptor DTF-IC is designed and synthesized in this work. The power conversion efficiency (PCE) of ternary OSCs increased up to 12.14% from 10.90% by incorporating 10â¯wt% of DTF-IC as second acceptors into the binary OSCs consisting of PBDB-T as donor and IT-M as acceptor. This was mainly due to the large increase in short-circuit current (Jsc) from 16.18 to 17.95â¯mA/cm2, without any drop in the open-circuit voltage (Voc) and fill factor (FF). The addition of DTF-IC enabled the donor and acceptor to form a distinct complementary absorption profile in the visible-light region, which boosted the photon harvesting in the range of 730-800â¯nm and consequently increased the Jsc of the ternary system by 11%. Moreover, there was an energy transfer between the two SM acceptors, favorable for enhancing charge separation and transfer as well as reducing charge recombination at PBDB-T:IT-M and PBDB-T:DTF-IC interface. Simultaneously, HOMO and LUMO energy levels of DTF-IC were lower than those of PBDB-T, but still higher than those of IT-M. Thus, DTF-IC is able to provide a cascading energy level with the host donor and acceptor which are beneficial for efficient charge transfer between the acceptors and facilitating exciton dissociation and carrier transport. Meanwhile, the highly crystalline DTF-IC as a third component can improve the crystallization process of the active layer while maintaining proper phase separation. This work proposes a novel idea for non-fullerene acceptors achieved via twin spiro-type structure modifying by indanone and provides a new direction for the selection of ternary solar cell materials.
ABSTRACT
Rational heteroatom engineering is applied to develop high-performance electron-transporting naphthalenediimide copolymers. Top-gate field-effect transistors fabricated from selenophene-containing polymers achieve an ultrahigh electron mobility of 8.5 cm2 V-1 s-1 and excellent air-stability. The results demonstrate that the incorporation of selenophene heterocycles into the polymers can improve the film-forming ability, intermolecular interaction, and carrier transport significantly.
ABSTRACT
Five-membered 1,3,4-oxadiazole (OZ) and 1,3,4-thiadiazole (TZ) heterocycle-based copolymers as active layer have long been ignored in solution-processable n-channel polymer field-effect transistors (PFETs) despite the long history of using OZ or TZ derivatives as the electron-injecting materials in organic light-emitting devices and their favorable electron affinities. Herein, we first report the synthesis and PFETs performance of two n-channel conjugated polymers bearing OZ- or TZ-based acceptor moieties, i.e., PNOZ and PNTZ, where simple thiophene units are utilized as the weak donors and additional alkylated-naphthalenediimides units are used as the second acceptors. A comparative study has been performed to reveal the effect of different heterocyclic acceptors on thermal properties, electronic properties, ordering structures, and carrier transport performance of the target polymers. It is found that both polymers possess low-lying LUMO values below -4.0 eV, indicating high electron affinity for both heterocycle-based polymers. Because of strong polarizable ability of sulfur atom in TZ heterocycle, PNTZ exhibits a red shift in maximal absorption and stronger molecular aggregation even in the diluted chlorobenzene solution as compared to the OZ-containing PNOZ. Surface morphological study reveals that a nodule-like surface with a rough surface morphology is observed clearly for PNOZ films, whereas PNTZ films display highly uniform surface morphology with well interconnected fiber-like polycrystalline grains. Investigation of PFETs performance indicates that both polymers afford air-stable n-channel transport characteristics. The uniform morphological structure and compact π-π stacking endow PNTZ with a high electron mobility of 0.36 cm2 V-1 s-1, much higher than that of PNOZ (0.026 cm2 V-1 s-1). These results manifest the feasibility in improving electron-transporting property simply by tuning heteroatom substitutes in n-channel polymers; further demostrate that TZ derivatives possess much superior potential for developing high-performance n-channel polymers compared to OZ derivatives.
ABSTRACT
A tandem directed metalation has been successfully applied to the preparation of thieno[2,3-f]benzofuran-4,8-dione, providing an efficient and facile approach to symmetrically and unsymmetrically functionalize the thieno[2,3-f]benzofuran core at the 2,6 positions as well as to introduce the electron-withdrawing or -donating groups (EWG or EDG) at its 4,8 positions. The presence of various functional groups makes late-stage derivatization attainable.
ABSTRACT
A novel conjugated side-chain polymer (PBDT-TID), based on benzo[1,2-b:4,5-b']dithiophene (BDT) and isoindigo (ID) moieties, was designed and synthesized. The new polymer exhibited excellent microphase separation in active layers. Bulk heterojunction polymer solar cells fabricated from PBDT-TID and PC61BM showed promising power conversion efficiencies of 5.25% and 6.51% using conventional and inverted device structures, respectively.
ABSTRACT
A new benzodithiophene-based copolymer PTG1 with dithienylbenzothiadiazole-vinylene side chains exhibits excellent film-forming ability, a deep HOMO energy level, and a good miscibility with PC(71)BM. Bulk heterojunction polymer solar cells fabricated from PTG1 and PC(71)BM showed a promising power conversion efficiency over 4.0%.
ABSTRACT
Three novel organic dyes based on porphyrin derivatives were designed and synthesized for dye-sensitized solar cells, resulting in a maximum power conversion efficiency (eta) of 5.14% and a maximum IPCE value of 72% for a cell based on the dye.
ABSTRACT
A series of block copolymers containing nonconjugated spacer and 3D pi-pi stacking structure with simultaneous blue-, green-, and yellow-emitting units has been synthesized and characterized. The dependence of the energy transfer and electroluminescence (EL) properties of these block copolymers on the contents of oligo(phenylenevinylene)s has been investigated. The block copolymer (GEO8-BEO-YEO4) with 98.8% blue-emitting oligomer (BEO), 0.8% green-emitting oligomer (GEO), and 0.4% yellow-emitting oligomer (YEO) showed the best electroluminescent performance, exhibiting a maximum luminance of 2309 cd/m(2) and efficiency of 0.34 cd/A. The single-layer-polymer light-emitting diodes device based on GEO2-BEO-YEO4 emitted greenish white light with the CIE coordinates of (0.26, 0.37) at 10 V. The synergetic effect of the efficient energy transfer and 3D pi-pi stack of these block copolymers on the photoluminescent and electroluminescent properties are investigated.