The role of material behavior in the performances of electroactive polymer energy harvesters

Electroactive polymer energy harvesters are promising devices for the conversion of mechanical work to electrical energy. The performances of these devices are strongly dependent on the mechanical response of the polymeric material and on the type of electromechanical cycle, and these are limited by the occurrence of dielectric breakdown, compression induced wrinkling and electromechanical instability (pull‐in). To identify the optimal electromechanical cycle that complies with all of these limitations, we set‐up and solve a constraint optimization problem and we critically discuss the influence of material behavior of the polymer in the optimal performances of the energy harvesting device. Finally, we show that if the rate‐independent dissipative behavior of the polymer (Mullins effect) is neglected, the optimization procedure may lead to quite unsatisfactory predictions: by making reference to explicit experimental data from literature we show that an optimal harvesting cycle deduced by neglecting the Mullins effect is far from being optimal when this is taken in consideration. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1303–1314     

Electrostrictive polymers for mechanical energy harvesting

This article reviews the developments in electrostrictive polymers for energy harvesting. Electrostrictive polymers are a variety of electroactive polymers that deform due to the electrostatic and polarization interaction between two electrodes with opposite electric charge. Electrostrictive polymers have been the subject of much interest and research over the past decade. In earlier years, much of the focus was placed on actuator configurations, and in more recent years, the focus has turned to investigating material properties that may enhance electromechanical activities. Since the last 5 years and with the development of low‐power electronics, the possibility of using these materials for energy harvesting has been investigated. This review outlines the operating principle in energy scavenging mode and conversion mechanisms behind this generator technology, highlights some of its advantages over existing actuator technologies, identifies some of the challenges associated with its development, and examines the main focus of research within this field, including some of the potential applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Enhanced electrostriction based on plasticized relaxor ferroelectric P(VDF‐TrFE‐CFE/CTFE) blends

The purpose of this work aims at enhancing the electrostrictive strain response and the mechanical energy density under moderate electric field, which is essential for actuator applications. For achieving this, plasticized effects as well as the influence of chlorofluoroethylene and chlorotrifluoroethylene defects on the electromechanical behavior of the copolymer matrix poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) are investigated. Experimental results showed that the plasticized terpolymer‐based CFE presented better electrical and mechanical performances than the CTFE one. Furthermore, such interesting properties exhibited superior advantages when CFE was combined with (DEHP) plasticizer, resulting in excellent electrostrictive strain response as well as mechanical energy density. Another aspect of this work reports on the influence of the composition, especially the CTFE content, on the electromechanical properties of the neat and plasticized P(VDF‐TrFE‐CTFE). This enables the determination of the desired terpolymer compositions for given applications, which are based on different criteria, such as crystallinity, elastic modulus, dielectric permittivity, and so forth. All the results demonstrated a possibility to realize high performance electroactive polymer actuators while achieving significant improved strain response and energy density under relatively low electric field. Such an investigation allows overcoming the current technological barrier of conventional electroactive polymers that suffer from the high applied electric field usually required to reach sufficient strain. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1368–1379     

萘酰亚胺-卟啉星型电子受体分子的构筑及其在非富勒烯太阳能电池中的应用

非富勒烯太阳能电池目前已经成为有机太阳能电池的研究热点,大量的共轭电子受体分子被开发,并成功应用到高性能光伏器件中。共轭分子作为非富勒烯电子受体,需要综合考虑吸收、能级、电子传输以及结晶性等,其中宽吸收光谱可以提高对太阳光谱的利用,是分子设计中重要因素之一。本工作中,我们设计一种新型电子受体分子,以卟啉为核、萘酰亚胺为端基以及炔为桥连基团。这种新型分子具有近红外的吸收光谱以及合适的能级。将一种具有吸收互补的共轭聚合物为电子给体,星型分子为电子受体应用到电池的活性层中,我们获得了1.8%的能量转换效率,电池的光谱响应为300–900 nm。实验结果证明了这种以卟啉为核的分子设计在实现近红外吸收的电子受体方面具有重要应用前景。     

Influence of Plasticizers on the Electromechanical Behavior of a P(VDF‐TrFE‐CTFE) Terpolymer: Toward a High Performance of Electrostrictive Blends

This work aims at providing a complete analysis of the effect of plasticizers on the electrostrictive terpolymer performance. To achieve this, several plasticizing agents such as 2‐ethylhexyl phtalate (DEHP), diisononyl phtalate (DINP), and palamoll 652 have been incorporated in the polymer matrix. Experimental results demonstrate that the proposed novel materials exhibited excellent electromechanical enhancement in terms of transverse strain and mechanical energy density under a moderate electric field, which is definitively critical in recent microscale actuation. Another objective of this article was to explore material characteristics as a function of the DINP content, and it was found that the plasticizer weigh fraction was the key parameter determining performance of the modified fluorinate terpolymer blends. Accordingly, it was revealed that high performance flexible actuators can be achieved merely by employing a simple and cheap plasticizer, thus making it possible to overcome the current technological barrier of conventional electroactive polymers that suffer from the high applied electric field usually required to reach sufficient strain. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 355–369     

LIGHT ABSORPTION AND ENERGY TRANSFER IN POLYENE-PORPHYRIN ESTERS*

Two examples of a new class of compounds, polyenes covalently linked to meso-tetraarylporphyrins, have been prepared. Optical studies revealed that energy transfer from a 26 π electron polyene moiety to the porphyrin was zero, whereas energy transfer efficiency from a polyene containing 18 π electrons was ?80%. The results demonstrate that the polyene moiety can function as an efficient light gathering antenna for possible application to porphyrin-based solar energy conversion schemes. In addition, such polyene-porphyrin esters may serve as probes of the structural requisites for light harvesting by carotenoids in the photosynthetic membranes of green plants.     

Benzodithiophene-Fused Perylene Bisimides as Electron Acceptors for Non-Fullerene Organic Solar Cells with High Open-Circuit Voltage

Tandem-junction organic solar cells require solar cells with visible light photo-response as front cells, in which an open-circuit voltage (V_oc) above 1.0 V is highly demanded. In this work, we are able to develop electron acceptors to fabricate non-fullerene organic solar cells (NFOSCs) with a very high V_oc of 1.14 V. This was realized by designing perylene bisimide (PBI)-based conjugated materials fused with benzodithiophene, in which Cl and S atom were introduced into the molecules in order to lower the frontier energy levels. The fused structures can reduce the aggregation of PBI unit and meanwhile maintain a good charge transport property. The new electron acceptors were applied into NFOSCs by using Cl and S substituted conjugated polymers as electron donor, in which an initial power conversion efficiency of 6.63 % and a high V_oc of 1.14 V could be obtained. The results demonstrate that the molecular design by incorporating Cl and S atom into electron acceptors has great potential to realize high performance NFOSCs.     

Coupling of methane under pulse corona plasma (I)

At normal temperature and pressure, pulse corona plasma was used as a new method for the dehydrogenative coupling of methane in the absence of oxygen. The effects of voltage polarity and input energy on the dehydrogenative coupling of methane were investigated. The parameter “energy efficiency” was introduced to examine the coupling of the input energy and the dehydrogenative coupling of methane. The experimental results show that positive corona gives higher energy efficiency than negative corona. When the positive corona was chosen, C₂ yield per pass was 31.6% and acetylene yield per pass was 30.1% with 44.6% methane conversion at an input energy density of 1788kJ/mol and a pulse repetition frequency of 66Hz. The function of input energy density towards methane conversion may be expressed as a formula of-In(1-X) =k (PIF). In the range of input energy employed, C₂ yield is proportional to input energy density, but energy efficiency drops off with increasing input energy density.     

Mechanochemical energy conversion of neutral polymer gels

Mechanochemical energy conversion exhibited by water-swollen poly(vinyl alcohol) gels has been studied. The effective mechanical work produced as well as the chemical energy converted were measured simultaneously. It is shown theoretically and experimentally that the mechanical work developed during the swelling of the mechanochemical system increases with increase of the external load (m), the degree of cross-linking (DC) and the deswelling ratio (ϕ/ϕ_e, i.e. the ratio of the volume fraction of network polymer (ϕ) to that of the same gel in equilibrium with pure diluent (ϕ_e)). The chemical energy converted was found to be practically independent of m. The efficiency of energy conversion increased with increase of m and DC, and significantly decreased with increase of ϕ/ϕ_e. Comparison is made between theoretical predictions and experimental findings.     

Improvement in energy conversion of electrostrictive composite materials by new approach via piezoelectric effect: Modeling and experiments

This study proposes a new model that couples the piezoelectric and electrostrictive behavior to minimize the polarization power of composite polymer. The development of this model is capable to predict the energy harvesting abilities of an electrostrictive composite. To improve the dielectric permittivity of electrostrictive polymer, the particles of PZT have been incorporated in order to increase the conversion efficiency of the composite. Dielectric characterization tests showed an increase in dielectric permittivity by a factor of 4.5 compared to pure polymer. Experimental measurements of harvested power validate the analytical model and demonstrate a good correlation between the two data. An equivalent of an electrical scheme has been developed, which allows modeling the two behaviors. The harvested power density under low frequency at 2% of strain can reach 0.30 μW/cm³ for 33% of PZT without the polarization field, including the conversion efficiency becomes higher. The energy harvester property of this material composite has excellent potential for several self‐powered applications such as wireless sensor networks and the internet of things.     

Combination of pi and Golden Ratio in Lennard–Jones-Type and Morse-Type Potential Energy Functions

This paper tests the validity of a Lennard–Jones-type and Morse-type potential functions, consisting a combination of pi and golden ratio constants, for describing intermolecular and interatomic interaction energy. The adjustable parameter, n, can be obtained based on experimental data near the minimum well-depth or by parametric conversion from other established potential functions. The remarkably good correlation of the proposed potential functions with experimental data and other potential functions reveal an intriguing property of the relationship between pi and golden ratio within the context of chemistry.     

Unraveling the Efficiency of Thioxanthone Based Triplet Sensitizers: A Detailed Theoretical Study

Photochemical activation by triplet photosensitizers is highly expedient for a green focus society. In this work, we have theoretically probed excited state characteristics of thioxanthone and its derivatives for their triplet harvesting efficiency using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Absorption and triplet energies corroborate well with the available experimental data. Our results predict that both the S₁ and T₁ states are π-π^* in nature, which renders a high oscillator strength for S₀ to S₁ transition. Major triplet exciton conversion occurs through intersystem crossing (ISC) channel between the S₁ (¹π-π^*) and high energy ³n- π^* state. Apart from that, there is both radiative and non-radiative channel from S₁ to S₀, which competes with the ISC channel and reduces the triplet harvesting efficiency. For thioxanthones with −OMe (Me=Methyl) or −F substitution at 2 or 2’ positions, the ISC channel is not energetically feasible, causing sluggish intersystem crossing quantum yield (Φ_ISC). For unsubstituted thioxanthone and for isopropyl substitution at 2’ position, the S₁-T₁ gap is slightly positive ( ), rendering a lower triplet harvesting efficiency. For systems with −OMe or −F substitution at 3 or 3’ position of thioxanthone, because of buried π state and high energy π^* state, the S₁-³nπ^* gap becomes negative. This leads to a high Φ_ISC (>0.9), which is key to being an effective photocatalyst.     

A Rechargeable Al/S Battery with an Ionic‐Liquid Electrolyte

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite‐free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg^?1) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlS_x. Herein, we demonstrate the first reversible Al/S battery in ionic‐liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid‐state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid‐state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system.     

Reversible peptide folding: Dependence on molecular force field used

Temperature‐dependent nuclear magnetic resonance (NMR) and CD spectra of methanol solutions of a β‐heptapeptide have been interpreted in such a way that the secondary structure, a 3₁₄‐helix, is assumed to be stable in a temperature range of between 298 and 393 K. This is in contrast to the results of a 50‐ns molecular dynamics simulation using the GROMOS 96 force field, which found a melting temperature of about 340 K. This discrepancy is addressed by further computational studies using the OPLS‐AA force field. The conformational energetics of N‐formyl‐3‐aminobutanamide in vacuo are obtained using ab initio and density functional quantum‐mechanical calculations at the HF/6‐31G*, B3LYP/6‐31G*, and B3LYP/6‐311+G* levels of theory. The results permit development of torsional parameters for the OPLS‐AA force field that reproduce the conformational energetics of the monomer. By varying the development procedure, three parameter sets are obtained that focus on reproducing either low‐energy or high‐energy conformations. These parameter sets are tested by simulating the reversible folding of the β‐heptapeptide in methanol. The melting temperature of the helix formed (>360 K) is found to be higher than the one obtained from simulations using the GROMOS 96 force field (∼340 K). Differences in the potential energy functions of the latter two force fields are evaluated and point to the origins of the difference in stability. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 774–787, 2000     

应用于染料敏化太阳能电池的基于染料R6的含有不同吸电子基团的有机染料的理论研究

Dye-sensitized solar cells (DSSCs) are the most promising alternatives to traditional fossil energy because of their advantages of low production cost, facile structure, relatively low environmental impact, relatively high photoelectronic absorption efficiency, and overall high efficiency. In addition, several studies on sensitizers as vital components have been conducted over the last three decades. Compared to metal dyes, metal-free organic dyes have been considered as promising candidates because of their simple fabrication, multiple structures, high molar absorption coefficients, easily tunable properties, and environmental friendliness. In this study, we systematically investigated the optoelectronic properties of six metal-free organic donor-acceptor dyes (RD1–6) derived from the known dye R6 by using the density functional theory (DFT) and time-dependent DFT methods. Cell performance parameters were discussed, including the geometrical and electronic structures, absorption spectrum, adsorption energy, light harvesting efficiency (LHE) curve, predictive short circuit current density (J_sc^Pred.), predictive open circuit voltage (V_oc^Pred.), and theoretical power conversion efficiency (PCE). Results revealed that all the designed dyes exhibited high theoretical PCE. In particular, dyes RD1, 2, and 4–6 showed greater conjugations, and dyes RD1–3 had smaller energy gaps than those of the reference dye. In addition, dyes RD1–3, 5, and 6 exhibited better light harvesting capacities that covered the entire visible region and extended to the near-infrared region with obviously red-shift maximum absorption wavelengths (λ_max), wider LHE curves, and higher J_sc^Pred. as compared to the reference dye. It was critical that dyes RD1 and 2 not only have greater conjugations and narrow band gaps but also good light harvesting capacities with more than 56-nm red-shift maximum absorption wavelengths and broadened LHE curves than those of the reference dye. Notably, mainly because of an average increment of 12.0% of J_sc^Pred., a remarkable increment of the theoretical power conversion efficiency was observed from 12.6% for dye R6 to 14.1% for dyes RD1 and 2. Thus, dyes RD1 and 2 exhibited superior cell performances and could be promising sensitizer candidates for highly efficient DSSCs. These results could be used to guide effective synthetic efforts in the discovery of efficient metal-free organic dye sensitizers in DSSCs.     

Enhanced Light‐Harvesting Capacity by Micellar Assembly of Free Accessory Chromophores and LH1‐like Antennas

Biohybrid light‐harvesting antennas are an emerging platform technology with versatile tailorability for solar‐energy conversion. These systems combine the proven peptide scaffold unit utilized for light harvesting by purple photosynthetic bacteria with attached synthetic chromophores to extend solar coverage beyond that of the natural systems. Herein, synthetic unattached chromophores are employed that partition into the organized milieu (e.g. detergent micelles) that house the LH1‐like biohybrid architectures. The synthetic chromophores include a hydrophobic boron‐dipyrrin dye (A1) and an amphiphilic bacteriochlorin (A2), which transfer energy with reasonable efficiency to the bacteriochlorophyll acceptor array (B875) of the LH1‐like cyclic oligomers. The energy‐transfer efficiencies are markedly increased upon covalent attachment of a bacteriochlorin (B1 or B2) to the peptide scaffold, where the latter likely acts as an energy‐transfer relay site for the (potentially diffusing) free chromophores. The efficiencies are consistent with a Förster (through‐space) mechanism for energy transfer. The overall energy‐transfer efficiency from the free chromophores via the relay to the target site can approach those obtained previously by relay‐assisted energy transfer from chromophores attached at distant sites on the peptides. Thus, the use of free accessory chromophores affords a simple design to enhance the overall light‐harvesting capacity of biohybrid LH1‐like architectures.     

Exploring the effect of different coumarin donors on the optical and photovoltaic properties of azo-bridged push-pull systems: A theoretical approach

We report the theoretical modeling of various azo-bridged coumarin-purpurin systems. The effect of varying the donor (coumarin) part of this D-π-D-π-A system was analyzed in terms of opto-electronic and photovoltaic parameters such as HOMO, LUMO, HOMO-LUMO energy gap, λ_max, light harvesting efficiency, charge injection efficiency, open voltage, reorganization energy by employing density functional theory as incorporated in Gaussian 03 set of codes. The dye-TiO₂ adsorbed systems were also studied using the same level of theory. It was found that just by varying the donor, although of same nature, there is a marked effect on the efficiency parameters of the dye sensitized solar cells based on such dyes. Also, the dye molecules were found to be good sensitizers for TiO₂ semiconductors.     

Triplet–Triplet Annihilation Upconversion for Photocatalytic Hydrogen Evolution

The solar generation of hydrogen by water splitting provides a promising path for renewable hydrogen production and solar energy storage. Upconversion of low-energy photons into high-energy photons constitutes a promising strategy to enhance the light harvesting efficiency of artificial hydrogen production systems. In the present study, upconversion micelles are integrated with Cd_0.5Zn_0.5S to construct solar energy conversion systems. The upconversion micelle is employed to upconvert red photons to cyan photons. Cd_0.5Zn_0.5S is sensitized by upconverted cyan light to produce hydrogen, but not by incident red light without triplet–triplet annihilation upconversion (TTA-UC). The performance of the upconversion photocatalytic system was dramatically affected by the concentration of Cd_0.5Zn_0.5S and the irradiation intensity. This novel system was able to produce about 2.3 μL hydrogen after 5 h of red light (629 nm) irradiation (2.4 mW cm⁻²). The present study provides a candidate for applications using low-energy photons for solar hydrogen generation.     

Environmentally Benign and Efficient Ag2S‐ZnO Nanowires as Photoanodes for Solar Cells: Comparison with CdS‐ZnO Nanowires

In this work, we develop a low‐temperature, facile solution reaction route for the fabrication of quantum‐dot‐sensitized solar cells (QDSSCs) containing Ag₂S‐ZnO nanowires (NWs), simultaneously ensuring low manufacturing costs and environmental safety. For comparison, a CdS‐ZnO NW photoanode was also prepared using the layer‐by‐layer growth method. Ultraviolet photoelectron spectroscopy analysis revealed type‐II band alignments for the band structures of both photoanodes which facilitate electron transfer/collection. Compared to CdS‐ZnO QDSSCs, Ag₂S‐ZnO QDSSCs exhibit a considerably higher short‐circuit current density (J_sc) and a strongly enhanced light‐harvesting efficiency, but lower open‐circuit voltages (V_oc), resulting in almost the same power‐conversion efficiency of 1.2 %. Through this work, we demonstrate Ag₂S as an efficient quantum‐dot‐sensitizing material that has the potential to replace Cd‐based sensitizers for eco‐friendly applications.