Photo-Rechargeable Asymmetric Supercapacitors Exceeding Light-to-Charge Storage Efficiency over 21% under Indoor Light.

Photo-rechargeable energy storage devices are appealing for substantial research attention because of their possible applications in the Internet of Things (IoT) and low-powered miniaturized portable electronics. However, due to the incompatibility of the photovoltaics and energy storage systems (ESSs), the overall light-to-storage efficiency is limited under indoor light conditions. Herein, a porous carbon scaffold MnO-Mn3 O4 /C microsphere-based monolithic dye-sensitized photo-rechargeable asymmetric supercapacitor (DSPC) is fabricated. The integrated DSPC has a high areal specific capacitance of 281.9 mF cm-2 at the discharge rate of 0.01 mA cm-2 . The light-to-electrical conversion efficiency of the DSSC is 27.6% under the 1000 lux compact fluorescent lamp (CFL). The DSPC shows an outstanding light-to-charge storage efficiency of 21.6%, which is higher than that reported ever. Furthermore, the fabricated polymer gel electrolyte-based quasi-solid state (QSS) DSPC shows similar overall conversion efficiency with superior cycling capability. This work shows a convenient fabrication process for a wireless power pack of interest with outstanding performance.

Synergistic Effect of Size-Tailored Structural Engineering and Postinterface Modification for Highly Efficient and Stable Dye-Sensitized Solar Cells.

Despite significant progress in device performance, dye-sensitized solar cells (DSSCs) continue to fall short of their theoretical potential. Moreover, research in recent years needs to pay more attention to improving the device fabrication process. To achieve the theoretical efficiency limit, it is crucial to optimize the interface between the dye and TiO2 nanoparticles in the entire device stack. Our study indicates that optimizing the structure or size of the coadsorbents and implementing a monolayer adsorption process can be an effective strategy to reduce charge recombination and enhance light-harvesting properties. Our research aims to develop a surface-coating adsorbent plan that controls the TiO2 nanoparticle interface to achieve the radiative limit of power conversion efficiency (PCE). Specifically, we utilized 2-thiophenecarboxylic acid (THCA) or chenodeoxycholic acid (CDCA) as postinterfacial surface-coating adsorbents. Our results demonstrate that this approach effectively achieves the desired PCE limit. Combined with the coadsorbent structure engineering and interface optimization, the device increased the packing area on the TiO2 nanoparticles' surface, reaching an improved PCE of over 13.17% under simulated sunlight (1.5G), which is the highest efficiency of a porphyrin single dye-based DSSC. In particular, this practical approach was also applied to a large-area DSSC with an area of 3 cm2, yielding a remarkable PCE of 9.04%. Furthermore, when applied to a polymer gel electrolyte, this novel approach recorded the highest PCE of 11.16% with a long-term operational stability of up to 1000 h for the quasi-solid-state DSSCs. Our research findings provide a promising avenue for achieving high-performance DSSCs with ease of access and demonstrate practical applications as alternatives to conventional power sources.

D-π-A Structured Porphyrin and Organic Dyes with Easily Synthesizable Donor Units for Low-Cost and Efficient Dye-Sensitized Solar Cells.

This study aimed to develop low-cost D-π-A structured porphyrin and organic dyes with easily synthesizable donor units instead of the conventional complex multistep synthetic donor unit of Hexyloxy-BPFA [bis(7-(2,4-bis(hexyloxy)phenyl)-9,9-dimethyl-9H-fluoren-2-yl)amine] used in SGT-021 and SGT-149 as well-known record cosensitizers with an extremely high power conversion efficiency (PCE). The design strategy concerned the easier synthesis of low-cost donor units with inversion structures in donor groups via donor structural engineering, particularly by changing the position of the fluorene and phenylene units in the donor moiety while keeping the π-bridge and acceptor unit unchanged, leading to the synthesis of two D-π-A structured porphyrins [SGT-021(D0) and SGT-021(D)] and one D-π-A structured organic sensitizer [SGT-149(D)] for dye-sensitized solar cells (DSSCs). Specifically, porphyrin SGT-021(D0) incorporated two hexyl chains into the 9-position of each fluorene, while SGT-021(D) and SGT-149(D) substituted two hexyloxy chain units to the terminal position of each fluorene in the donor groups of porphyrin dyes. The effect of the position of the fluorene and phenylene units in the donor moiety on the photochemical and electrochemical properties, as well as the photovoltaic performance, was compared with the reference dyes of SGT-021 and SGT-149, previously reported by the research group. After optimizing the DSSC devices, SGT-021(D) and SGT-021(D0) achieved a high PCE of 11.6 and 10.5%, respectively, while SGT-149(D) exhibited a little lower PCE of 10.3% under the standard AM 1.5G light intensity. The cell performance of DSSC devices based on SGT-021(D) and SGT-149(D) was inferior to the corresponding reference dyes of SGT-021 and SGT-149 due to their lower donating ability of Hexyloxy-BPFA than Hexyloxy-BFPA.

Redox Shuttle-Based Electrolytes for Dye-Sensitized Solar Cells: Comprehensive Guidance, Recent Progress, and Future Perspective.

A redox electrolyte is a crucial part of dye-sensitized solar cells (DSSCs), which plays a significant role in the photovoltage and photocurrent of the DSSCs through efficient dye regeneration and minimization of charge recombination. An I-/I3 - redox shuttle has been mostly utilized, but it limits the open-circuit voltage (V oc) to 0.7-0.8 V. To improve the V oc value, an alternative redox shuttle with more positive redox potential is required. Thus, by utilizing cobalt complexes with polypyridyl ligands, a significant power conversion efficiency (PCE) of above 14% with a high V oc of up to 1 V under 1-sun illumination was achieved. Recently, the V oc of a DSSC has exceeded 1 V with a PCE of around 15% by using Cu-complex-based redox shuttles. The PCE of over 34% in DSSCs under ambient light by using these Cu-complex-based redox shuttles also proves the potential for the commercialization of DSSCs in indoor applications. However, most of the developed highly efficient porphyrin and organic dyes cannot be used for the Cu-complex-based redox shuttles due to their higher positive redox potentials. Therefore, the replacement of suitable ligands in Cu complexes or an alternative redox shuttle with a redox potential of 0.45-0.65 V has been required to utilize the highly efficient porphyrin and organic dyes. As a consequence, for the first time, the proposed strategy for a PCE enhancement of over 16% in DSSCs with a suitable redox shuttle is made by finding a superior counter electrode to enhance the fill factor and a suitable near-infrared (NIR)-absorbing dye for cosensitization with the existing dyes to further broaden the light absorption and enhance the short-circuit current density (J sc) value. This review comprehensively analyzes the redox shuttles and redox-shuttle-based liquid electrolytes for DSSCs and gives recent progress and perspectives.

Influence of the π-Bridge-Fused Ring and Acceptor Unit Extension in D-π-A-Structured Organic Dyes for Highly Efficient Dye-Sensitized Solar Cells.

Three new D-π-A-structured organic dyes, coded as SGT-138, SGT-150, and SGT-151, with the expansion of π-conjugation in the π-bridge and acceptor parts have been developed to adjust HOMO/LUMO levels and to expand the light absorption range of organic dyes. Referring to the SGT-137 dye, the π-bridge group was extended from the 4-hexyl-4H-thieno[3,2-b]indole (TI) to the 9-hexyl-9H-thieno[2',3':4,5]thieno[3,2-b]indole (TII), and the acceptor group was extended from (E)-3-(4-(benzo[c][1,2,5]thiadiazol-4-yl)phenyl)-2-cyanoacrylic acid (BTCA) to (E)-3-(4-(benzo[c][1,2,5]thiadiazol-4-ylethynyl)phenyl)-2-cyanoacrylic acid (BTECA), where TII was introduced as a π-bridging unit for the first time. It was determined that both extensions are promising strategies to enhance the light-harvesting ability. They present several features, such as (i) efficiently intensifying the extinction coefficient and expanding the absorption bands; (ii) exhibiting enhanced intramolecular charge transfer in comparison with the SGT-137; and (iii) being favorable to photoelectric current generation of dye-sensitized solar cells (DSSCs) with cobalt electrolytes. In particular, the π-spacer extension from TI to TII was useful for modulating the HOMO energy levels, while the acceptor extension from BTCA to BTECA was useful for modulating the LUMO energy levels. These phenomena could be explained with the aid of density functional theory calculations. Finally, the DSSCs based on new SGT-dyes with an HC-A1 co-adsorbent presented good power conversion efficiencies as high as 11.23, 11.30, 11.05, and 10.80% for SGT-137, SGT-138, SGT-150, and SGT-151, respectively. Furthermore, it was determined that the use of the bulky co-adsorbent, HC-A1, can effectively suppress the structural relaxation of dyes in the excited state, thereby enhancing the charge injection rate of SGT-dyes. The observations in time-resolved photoluminescence were indeed consistent with the variation in the PCE, quantitatively.

Well-dispersed Te-doped mesoporous carbons as Pt-free counter electrodes for high-performance dye-sensitized solar cells.

A tellurium-doped carbon nanomaterial (Te-MC(P)) was newly developed by the soft-templated carbonization of the PAN-b-PBA copolymer with poly(3-hexyltellurophene). Te-MC(P) was characterized with various characterization methods, including the nitrogen sorption isotherm measurement (BET), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDS), which reveal that the Te atoms are homogeneously dispersed in the three-dimensional hierarchical, graphite-like mesoporous carbon matrix with a Te doping level of 0.27 atom %. Based on the characterization results, the electrocatalytic ability of Te-MC(P) was evaluated by using a symmetrical dummy cell test with both Co(bpy)32+/3+ (bpy = 2,2'-bipyridine) and I-/I3- redox electrolytes as counter electrodes (CEs). The Te-MC(P) CEs showed remarkably lower charge-transfer resistance (Rct) values by approximately 10 times in the electrochemical impedance spectroscopy (EIS) measurement, compared to the counterpart platinum (Pt) and the tellurium-based material (Te-MC(A)), prepared with a telluric acid precursor that has a lower Te doping level of 0.15 at%. As a result, the excellent electrocatalytic ability of Te-MC(P) resulted in the improvement of photovoltaic performance. The power conversion efficiencies (PCEs) of Te-MC(P)-based dye-sensitized solar cells (DSSCs) were 12.69% for the Co(bpy)32+/3+ redox electrolyte with the SGT-021 porphyrin dye and 9.73% for the I-/I3- redox electrolyte with the N719 ruthenium dye. Furthermore, Te- MC(P) CEs exhibited remarkable electrochemical stability in the two redox electrolytes. These results could suggest that the Te-MC(P) CE is one of the best promising alternatives to Pt CEs as a low-cost, highly stable and efficient electrocatalytic CE for practical applications.

Mechanism for Preserving Volatile Nitrogen Dioxide and Sustainable Redox Mediation in the Nonaqueous Lithium-Oxygen Battery.

Excessive overpotential during charging is a major hurdle in lithium-oxygen (Li-O2) battery technology. NO2-/NO2 redox mediation is an efficient way to substantially reduce the overpotential and to enhance oxygen efficiency and cycle life by suppressing parasitic reactions. Considering that nitrogen dioxide (NO2) is a gas, it is quite surprising that NO2-/NO2 redox reactions can be sustained for a long cycle life in Li-O2 batteries with such an open structure. A detailed study with in situ differential electrochemical mass spectrometry (DEMS) elucidated that NO2 could follow three reaction pathways during charging: (1) oxidation of Li2O2 to evolve oxygen, (2) vaporization, and (3) conversion into NO3-. Among the pathways, Li2O2 oxidation occurs exclusively in the presence of Li2O2, which suggests that NO2 has high reactivity to Li2O2. At the end of the charging process, most of the volatile oxidized couple (NO2) is stored by conversion to a stable third species (NO3-), which is then reused for producing the reduced couple (NO2-) in the next cycle. The dominant reaction of Li2O2 oxidation involves the temporary storage of NO2 as a stable third species during charging, which is an innovative way for preserving the volatile redox couple, resulting in a sustainable redox mediation for a high-performance Li-O2 battery.

Three-dimensional tellurium and nitrogen Co-doped mesoporous carbons for high performance supercapacitors.

Tellurium-doped mesoporous carbon composite materials (Te/NMC) have been prepared by a facile intercalation method in the presence of nitrogen-doped mesoporous carbon (NMC) with tellurium powder, for the first time. The effects of the co-doped N and Te in the mesoporous carbon matrix on the physical/chemical properties and capacitance performances were investigated via the use of various characterization methods and electrochemical studies. The as-prepared NMC and Te/NMC materials were found to mainly be composed of mesopores and maintained the 3D hierarchical graphite-like structure with lots of defect sites. By intercalation of Te atoms into the NMC materials, 2.12 at% (atom%) of Te was doped into NMC and the specific surface area of Te/NMC (261.07 m2 g-1) decreased by about 1.5 times compared to that of NMC (437.96 m2 g-1). In electrochemical measurements as a supercapacitor (SC) electrode, the Te/NMC based electrode, even with its lower porosity parameters, exhibited a higher capacitive performance compared to the NMC-based electrode. These results for Te/NMC arise due to the pseudo-capacitive effect of doped Te and the increase in the capacitive area available from the formation of interconnections in the mesoporous carbons through Te-O bonds. As a result, the synergetic effect of the Te and N atoms enables Te/NMC to exhibit the highest specific capacitance of 197 F g-1 at a current density of 0.5 A g-1. Moreover, remarkable long-term cycling stability with the retention of more than 95% of the initial capacitance is observed for Te/NMC at a current density of 5 A g-1 and also for 1000 charge-discharge cycles.

The complete chloroplast genome of Douinia plicata (Lindb.) Konstant. & Vilnet (Scapaniaceae, Jungermanniales).

We completed chloroplast genome of Douinia plicata (Lindb.) Konstant. & Vilnet., presenting morphological features including denticulate leaf margin, verrucose cuticle on base of leaves, and 80-100° keel angle with stem at the midleaf. It is 118,797 bp long (GC ratio is 33.9%) and has four subregions: 81,142 bp of large single copy (31.9%) and 19,611 bp of small single copy (31.0%) regions are separated by 9,017 bp of inverted repeat (46.3%) regions including 130 genes (86 protein-coding genes, eight rRNAs, and 36 tRNAs). Phylogenetic trees show D. plicata is clustered with two Scapania species.

Polymer Gel Electrolytes Based on PEG-Functionalized ABA Triblock Copolymers for Quasi-Solid-State Dye-Sensitized Solar Cells: Molecular Engineering and Key Factors.

The molecular weights and structural properties of polymers play key roles in the efficiency of gelators in polymer gel electrolytes (PGEs) for quasi-solid-state dye-sensitized solar cells (QSS-DSSCs). To find an appropriate gelator, we synthesized well-defined poly(acrylonitrile-co-N,N-dimethylacrylamide)-block-poly(ethylene glycol)-block-poly(acrylonitrile-co-N,N-dimethylacrylamide) ABA triblock copolymers with various molecular weights and copolymer compositions by reversible addition-fragmentation chain-transfer polymerization. The ratio of acrylonitrile (AN)/N,N-dimethylacrylamide (DMAA) in the triblock copolymers influences their solubility in liquid electrolytes (LEs) and thermal stability. The highest thermal stability was up to 360 °C, and this was achieved by the polymer with an AN/DMAA ratio of ≤4. The thermal stability was related to excessive randomness in the P(AN-co-DMAA) block that hinders cyclization among nitrile groups. Both the molecular weights and the AN/DMAA ratios enabled gel formation by controlling the amount of the polymer, and hence, they influence the ionic conductivity and diffusion as well. Based on the electrochemical properties, polymers with molecular weights above 100 kg/mole were efficient as PGEs in QSS-DSSCs. The overall power conversion efficiency (PCE) of 14 wt % SGT-626 PGE-based QSS-DSSCs was 9.72% under AM 1.5G solar illumination, comparable with an overall PCE of 9.79% for LE DSSCs. The overall PCE of the QSS-DSSCs further increased to 10.02% by incorporating 3 wt % TiO2 nanoparticles in the 14 wt % SGT-626 PGE. The SGT-626 PGE-based QSS-DSSC was also tested under indoor light conditions, and the best PCE of 21.26% was achieved under a white LED light of 1000 lux, which is higher than the PCE of 19.94% for the LE DSSC. The long-term device stability test under adverse conditions (50 °C and 1 sun illumination) reveals the improved stability of PGE-based QSS-DSSCs over LE DSSCs. In terms of PCE and long-term device stability, our PGE QSS-DSSCs have great potential over LE DSSCs for future indoor and outdoor applications.

Recent progress on nanostructured carbon-based counter/back electrodes for high-performance dye-sensitized and perovskite solar cells.

Dye-sensitized solar cells (DSSCs) and perovskite solar cells (PSCs) favor minimal environmental impact and low processing costs, factors that have prompted intensive research and development. In both cases, rare, expensive, and less stable metals (Pt and Au) are used as counter/back electrodes; this design increases the overall fabrication cost of commercial DSSC and PSC devices. Therefore, significant attempts have been made to identify possible substitutes. Carbon-based materials seem to be a favorable candidate for DSSCs and PSCs due to their excellent catalytic ability, easy scalability, low cost, and long-term stability. However, different carbon materials, including carbon black, graphene, and carbon nanotubes, among others, have distinct properties, which have a significant role in device efficiency. Herein, we summarize the recent advancement of carbon-based materials and review their synthetic approaches, structure-function relationship, surface modification, heteroatoms/metal/metal oxide incorporation, fabrication process of counter/back electrodes, and their effects on photovoltaic efficiency, based on previous studies. Finally, we highlight the advantages, disadvantages, and design criteria of carbon materials and fabrication challenges that inspire researchers to find low cost, efficient and stable counter/back electrodes for DSSCs and PSCs.

Dopant-Free Triazatruxene-Based Hole Transporting Materials with Three Different End-Capped Acceptor Units for Perovskite Solar Cells.

A series of dopant-free D-π-A structural hole-transporting materials (HTMs), named as SGT-460, SGT-461, and SGT-462, incorporating a planner-type triazatruxene (TAT) core, thieno[3,2-b]indole (TI) π-bridge and three different acceptors, 3-ethylthiazolidine-2,4-dione (ED), 3-(dicyano methylidene)indan-1-one (DI), and malononitrile (MN), were designed and synthesized for application in perovskite solar cells (PrSCs). The effect of three acceptor units in star-shaped D-π-A structured dopant-free HTMs on the photophysical and electrochemical properties and the photovoltaic performance were investigated compared to the reference HTM of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD). Their highest occupied molecular orbital (HOMO) energy levels were positioned for efficient hole extraction from a MAPbCl3-xIx layer (5.43 eV). The hole mobility values of the HTMs without dopants were determined to be 7.59 × 10-5 cm2 V-1 s-1, 5.13 × 10-4 cm2 V-1 s-1, and 7.61 × 10-4 cm2 V-1 s-1 for SGT-460-, SGT-461-, and SGT-462-based films. The glass transition temperature of all HTMs showed higher than that of the spiro-OMeTAD. As a result, the molecular engineering of a planer donor core, π-bridge, and end-capped acceptor led to good hole mobility, yielding 11.76% efficiency from SGT-462-based PrSCs, and it provides a useful insight into the synthesis of the next-generation of HTMs for PrSC application.

In situ preparation of Ru-N-doped template-free mesoporous carbons as a transparent counter electrode for bifacial dye-sensitized solar cells.

The development of a highly active, long-lasting, and cost-effective electrocatalyst as an alternative to platinum (Pt) is a vital issue for the commercialization of dye-sensitized solar cells. In this study, Ru-N-doped template-free mesoporous carbon (Ru-N-TMC) was prepared by the direct stabilization and carbonization of the poly(butyl acrylate)-b-polyacrylonitrile (PBA-b-PAN) block copolymer and ruthenium(iii) acetylacetonate [Ru(acac)3]. During the stabilization process, microphase separation occurred in the PBA-b-PAN block copolymer due to the incompatibility between the two blocks, and the PAN block transformed to N-doped semi-graphitic carbon. In the carbonization step, the PBA block was eliminated as a porous template, creating hierarchal mesopores/micropores. Meanwhile, Ru(acac)3 was decomposed to Ru, which was homogeneously distributed over the carbon substrate and anchored through N and O heteroatoms. The resulting Ru-N-TMC showed ultra-low charge transfer resistance (Rct = 0.034 Ω cm2) in the Co(bipyridine)33+/2+ reduction reaction, indicating very high electrocatalytic ability. Even though it is a transparent counter electrode (CE, average visible transmittance of 42.25%), covering a small fraction of the fluorine doped tin oxide (FTO)/glass substrate with Ru-N-TMC, it led to lower charge transfer resistance (Rct = 0.55 Ω cm2) compared to Pt (Rct = 1.00 Ω cm2). The Ru-N-TMC counter electrode exhibited a superior power conversion efficiency (PCE) of 11.42% compared to Pt (11.16%) when employed in SGT-021/Co(bpy)33+/2+ based dye-sensitized solar cells (DSSCs). Furthermore, a remarkable PCE of 10.13% and 8.64% from front and rear illumination, respectively, was obtained when the Ru-N-TMC counter electrode was employed in a bifacial DSSC. The outstanding catalytic activity and PCE of Ru-N-TMC were due to the high surface area of Ru-N-TMC, which contained numerous active species (Ru and N), easily facilitated to redox ions through the hierarchical microporous/mesoporous structure.

Tellurium-Doped, Mesoporous Carbon Nanomaterials as Transparent Metal-Free Counter Electrodes for High-Performance Bifacial Dye-Sensitized Solar Cells.

Tellurium-doped, mesoporous carbon nanomaterials with a relatively high doping level were prepared by a simple stabilization and carbonization method in the presence of a tellurium metalloid. A transparent counter electrode (CE) was prepared using tellurium-doped, mesoporous carbon (TeMC) materials, and was directly applied to bifacial, dye-sensitized solar cells (DSSCs). To improve the performance of the bifacial DSSC device, CEs should have outstanding electrocatalytic activity, electrical conductivity, and electrochemical stability, as well as high transparency. In this study, to make transparent electrodes with outstanding electrocatalytic activity and electrical conductivity, various TeMC materials with different carbonization temperatures were prepared by simple pyrolysis of the polyacrylonitrile-block-poly (n-butyl acrylate) (PAN-b-PBA) block copolymer in the presence of the tellurium metalloid. The electrocatalytic activity of the prepared TeMC materials were evaluated through a dummy cell test, and the material with the best catalytic ability was selected and optimized for application in bifacial DSSC devices by controlling the film thickness of the CE. As a result, the bifacial DSSC devices with the TeMC CE exhibited high power conversion efficiencies (PCE), i.e., 9.43% and 8.06% under front and rear side irradiation, respectively, which are the highest values reported for bifacial DSSCs to date. Based on these results, newly-developed transparent, carbon-based electrodes may lead to more stable and effective bifacial DSSC development without sacrificing the photovoltaic performance of the DSSC device.

D-π-A-Structured Porphyrins with Extended Auxiliary π-Spacers for Highly Efficient Dye-Sensitized Solar Cells.

Zn(II)-porphyrin dyes (SGT-030 and SGT-031) with extended auxiliary π-spacers in the donor (D) part have been prepared and applied to dye-sensitized solar cells (DSSCs). The porphyrin dyes contained the same D-ethynyl-zinc porphyrinyl (ZnP)-ethynyl-benzothiadiazole-acceptor platform, but their donor groups varied from phenylene (Ph) in SGT-053 as a reference dye to the thieno[3,2-b]benzothiophene (TBT) and 4-hexyl-4H-thieno[3,2-b]indole (TI) moieties in SGT-030 and SGT-031, respectively. The effects of the extended auxiliary π-spacer in the D-π-A-structured porphyrin sensitizers on the molecular and photovoltaic properties were investigated via photophysical and electrochemical experiments as well as theoretical calculations. With the trend in conjugation length (Ph < TBT ≈ TI) and the donating ability of the π-spacer (Ph < TBT < TI), the absorption maxima and molecular absorptivity increased in the order SGT-053 (Ph) < SGT-030 (TBT) < SGT-031 (TI). The incorporation of TBT and TI promoted significant enhancements in the light-harvesting properties by reducing the energy gap and efficiently improving electronic communication. The DSSCs based on SGT-030 (10.80%) and SGT-031 (10.89%) with coadsorption of 4-(3,6-bis(4-((2-ethylhexyl)oxy)phenyl)-9H-carbazol-9-yl)benzoic acid in conjunction with the [Co(bpy)3]2+/3+-based electrolyte showed better power conversion efficiency than that of SGT-053 (9.10%). Electrochemical impedance spectroscopy analysis unveiled that the difference in Jsc and Voc originates mainly from the twisted orientation between D and ZnP by the introduction of TBT and TI. This result indicated that the introduction of an extended auxiliary π-spacer in the donor part is a rational molecular design approach to improve photovoltaic performance by enhancing the light-harvesting ability and hindering charge recombination on the TiO2 photoanode.

Phenothiazine Functionalized Multifunctional A-π-D-π-D-π-A-Type Hole-Transporting Materials via Sequential C-H Arylation Approach for Efficient and Stable Perovskite Solar Cells.

Three phenothiazine-based A-π-D-π-D-π-A-type small molecules containing various terminal acceptor units, which act as Lewis base blocks, have been synthesized via an efficient and step-economical, direct C-H arylation strategy in the aim toward the development of hole-transporting materials (HTMs) with multifunctional features (such as efficient hole extraction layer, trap passivation layer, and hydrophobic protective layer) for perovskite solar cells (PrSCs). Optical-electrochemical correlation and density functional theory studies reveal that dicyanovinylene acceptor in SGT-421 downshifted the highest occupied molecular orbital (HOMO) level (-5.41 eV), which is more proximal to the valence band (-5.43 eV) of the perovskite, whereas N-methyl rhodanine in SGT-420 and 1,3-indanedione (IND) in SGT-422 destabilized the HOMO, leading to an increased interfacial energy-level offset. SGT-421 exhibits superior properties in terms of a sufficiently low-lying HOMO level and favorable energy-level alignment, intrinsic hole mobility, interfacial hole transfer, hydrophobicity, and trap passivation ability over spiro-OMeTAD as a benchmark small-molecule HTM. As envisaged in the design concept, SGT-421-based PrSC not only yields a comparable efficiency of 17.3% to the state-of-art of spiro-OMeTAD (18%), but also demonstrates the enhanced long-term stability compared to the spiro-OMeTAD because of its multifunctional features. More importantly, the synthetic cost of SGT-421 is estimated to be 2.15 times lower than that of spiro-OMeTAD. The proposed design strategy and the study of acceptor-property relationship of HTMs would provide valuable insights into and guidelines for the development of new low-cost and efficient multifunctional HTMs toward the realization of efficient and long-term stable PrSCs.

Soft-Templated Tellurium-Doped Mesoporous Carbon as a Pt-Free Electrocatalyst for High-Performance Dye-Sensitized Solar Cells.

Among various photovoltaic devices, dye-sensitized solar cells (DSSCs) are one of the most potentially clean and renewable energy conversion devices because of their low fabrication cost, environmentally friendly nature, and high power conversion efficiency. However, the use of rare metals such as Pt counter electrodes (CEs) is one of the major drawbacks of DSSC devices for broad real-life applications. In this regard, alternative materials to Pt CEs have been long sought for DSSCs employing both cobalt and iodine redox couples. Therefore, in this study, soft-templated tellurium-doped mesoporous carbons (Te-SMCs) were synthesized for the first time by the simple pyrolysis of PAN- b-PBA block copolymer in the presence of a tellurium precursor for replacing the Pt CE. To confirm the chemical composition and porosity, the as-prepared Te-SMC materials were evaluated by elemental analysis (XPS and EDS) and nitrogen sorption isotherms measurement. The as-prepared Te-SMC materials contained mainly mesopores and retained the three-dimensional hierarchical graphite-like structure with many defect sites. They displayed doping levels with nitrogen of 9.15 atom % and tellurium of 0.15 atom % and had a specific surface area of 540 m2 g-1. Therefore, these characteristics enabled the development of a high-performance CE in DSSCs with cobalt and iodine redox couples. As a result of its catalytic performance, Te-SMC exhibited outstanding electrocatalytic activity as well as a significantly improved electrochemical stability than those of Pt CE for both redox couples even after 1000 potential cycles. The results show that a maximum conversion efficiency of 11.64 and 9.67% could be achieved under one sun illumination (AM 1.5G) for SGT-021/Co(bpy)32+/3+- and N719/I-/I3--based devices with Te-SMC CEs, and their power conversion efficiency is superior to the corresponding device with Pt CEs.

Significant Influence of a Single Atom Change in Auxiliary Acceptor on Photovoltaic Properties of Porphyrin-Based Dye-Sensitized Solar Cells.

The rational design of porphyrin sensitizers is always crucial for dye-sensitized solar cells (DSSCs), since the change of only a single atom can have a significant influence on the photovoltaic performance. We incorporated the pyridothiadiazole group, as a stronger electron-withdrawing group, into the commonly well-established skeleton of D-porphyrin-triple bond-acceptor sensitizers by a single atom change for a well-known strong electron-withdrawing benzothiadiazole (BTD) unit as an auxiliary acceptor. The impact of the pyridothiadiazole group on the optical; electrochemical; and photovoltaic properties of D⁻π⁻A porphyrin sensitizers was investigated with comparison for a benzothiadiazole-substituted SGT-020 porphyrin. The pyridothiadiazole-substituted SGT-024 porphyrin dye was red-shifted so that the absorption range might be expected to achieve higher light harvest efficiency (LHE) than the SGT-020 porphyrin. However, all the devices were fabricated by utilizing SGT-020 and SGT-024, evaluated and found to achieve a cell efficiency of 10.3% for SGT-020-based DSSC but 4.2% for SGT-024-based DSSC under standard global AM 1.5G solar light conditions. The main reason is the lower charge collection efficiency of SGT-024-based DSSC than SGT-020-based DSSC, which can be attributed to the tilted dye adsorption mode on the TiO2 photoanode. This may allow for faster charge recombination, which eventually leads to lower Jsc, Voc and power conversion efficiency (PCE).

High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

To fabricate a sustainable lithium-oxygen (Li-O2) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO3) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO3 electrolyte efficiently produces NO2-, which initiates a redox shuttle reaction. Interestingly, this NO2-/NO2 redox reaction derived from the LiNO3 salt is not very effective in solvents other than TMS. Compared with other common Li-O2 solvents, TMS seems optimum solvent for the efficient use of LiNO3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO2-/NO2 redox reaction, which results in a high-performance Li-O2 battery.

Edge-selenated graphene nanoplatelets as durable metal-free catalysts for iodine reduction reaction in dye-sensitized solar cells.

Metal-free carbon-based electrocatalysts for dye-sensitized solar cells (DSSCs) are sufficiently active in Co(II)/Co(III) electrolytes but are not satisfactory in the most commonly used iodide/triiodide (I(-)/I3 (-)) electrolytes. Thus, developing active and stable metal-free electrocatalysts in both electrolytes is one of the most important issues in DSSC research. We report the synthesis of edge-selenated graphene nanoplatelets (SeGnPs) prepared by a simple mechanochemical reaction between graphite and selenium (Se) powders, and their application to the counter electrode (CE) for DSSCs in both I(-)/I3 (-) and Co(II)/Co(III) electrolytes. The edge-selective doping and the preservation of the pristine graphene basal plane in the SeGnPs were confirmed by various analytical techniques, including atomic-resolution transmission electron microscopy. Tested as the DSSC CE in both Co(bpy)3 (2+/3+) (bpy = 2,2'-bipyridine) and I(-)/I3 (-) electrolytes, the SeGnP-CEs exhibited outstanding electrocatalytic performance with ultimately high stability. The SeGnP-CE-based DSSCs displayed a higher photovoltaic performance than did the Pt-CE-based DSSCs in both SM315 sensitizer with Co(bpy)3 (2+/3+) and N719 sensitizer with I(-)/I3 (-) electrolytes. Furthermore, the I3 (-) reduction mechanism, which has not been fully understood in carbon-based CE materials to date, was clarified by an electrochemical kinetics study combined with density functional theory and nonequilibrium Green's function calculations.