Donor-п-acceptor conjugated copolymers for photovoltaic applications : tuning the open-circuit voltage by adjusting the donor/acceptor ratio

A class of new conjugated copolymers containing a donor (thiophene)−acceptor (2-pyran-4-ylidene-malononitrile) was synthesized via Stille coupling polymerization. The resulting copolymers were characterized by 1H NMR, elemental analysis, GPC, TGA, and DSC. UV−vis spectra indicated that the increase in the content of the thiophene units increased the interaction between the polymer main chains to cause a red-shift in the optical absorbance. Cyclic voltammetry was used to estimate the energy levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) and the band gap (Eg) of the copolymers. The basic electronic structures of the copolymers were also studied by DFT calculations with the GGA/B3LYP function. Both the experimental and the calculated results indicated an increase in the HOMO energy level with increasing the content of thiophene units, whereas the corresponding change in the LUMO energy level was much smaller. Polymer photovoltaic cells of a bulk heterojunction were fabricated with the structure of ITO/PEDOT/PSS (30 nm)/copolymer−PCBM blend (70 nm)/Ca (8 nm)/Al (140 nm). It was found that the open-circuit voltage (Voc) increased (up to 0.93 V) with a decrease in the content of thiophene units. Although the observed power convention efficiency is still relatively low (up to 0.9%), the corresponding low fill factor (0.29) indicates considerable room for further improvement in the device performance. These results provided a novel concept for developing high Voc photovoltaic cells based on donor-π-acceptor conjugated copolymers by adjusting the donor/acceptor ratio.

A four-directional non-fullerene acceptor based on tetraphenylethylene and diketopyrrolopyrrole functionalities for efficient photovoltaic devices with a high open-circuit voltage of 1.18 V

Through the conjunction of tetraphenylethylene and diketopyrrolopyrrole functionalities, a novel four-directional non-fullerene electron acceptor (denoted as 4D) was designed, synthesized and characterized. The new chromophore is highly soluble (for instance >30 mg mL(-1) in o-dichlorobenzene), thermally stable, and exhibits energy levels matching those of the conventional and routinely used donor polymer poly(3-hexyl thiophene). A power conversion efficiency of 3.86% was obtained in solution-processable bulk-heterojunction devices with a very high open circuit voltage of 1.18 V.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

Double layer structure of ionic liquids at the Au(111) electrode interface : an atomic force microscopy investigation

The double layer structure of two ionic liquids (ILs), 1-butyl-1- methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py ₁,₄]FAP) and 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([EMIm]FAP) at the polarized Au(111) electrode interface is probed using Atomic Force Microscopy force measurements. The force-separation profiles suggest a multilayered morphology is present at the electrified Au(111)-IL interface, with more near surface layers detected at higher potentials. At the (slightly negative) open circuit potential, multiple ion layers are present, and the innermost layer, in contact with the Au(111) surface, is enriched in the cation due to electrostatic adsorption. Upon applying negative electrode potentials (-1.0 V, -2.0 V), stronger IL near surface structure is detected: both the number of ion layers and the force required to rupture these layers increases. Positive electrode potentials (+1.0 V, +2.0 V) also enhance IL near surface structure, but not as much as negative potentials, because surface-adsorbed anions are less effective at templating structure in subsequent layers than cations. This interfacial structure is not consistent with a double layer in the Stern-Gouy-Chapman sense, as there is no diffuse layer. The structure is consistent with a capicitative double-layer model, with a very small separation distance between the planes of charge.

Enhanced thermo-electrochemical power using carbon nanotube additives in ionic liquid redox electrolytes

Waste heat recovery with thermo-electrochemical cells is limited by their low power and conversion efficiencies. Here we explore ionic liquid electrolytes mixed with multiwall carbon nanotubes (MWCNTs) as alternative electrolytes for thermo-electrochemical cells. The results show that, upon addition of MWCNTs, the combination of interfacial polarization and ion pair dissociation reduces mass transfer resistances and enhances the power of thermo-electrochemical cells at low weight percentage of MWCNTs by up to 30%. This occurs in spite of reduced open circuit voltage due to percolated networks.

A comprehensive analytical subdomain model and its field solutions for surface-mounted permanent magnet machines

This paper presents a comprehensive analytical subdomain model together with its field solutions for predicting the magnetic field distributions in surface-mounted permanent magnet (PM) machines. The tooth tips and slotting effects during open-circuit, armature reaction, and on-load conditions are considered when deriving the model and developing its solutions. The model derivations and field solutions are extended from a previous model, and can be applied to PM machines with any combinations of slot and pole numbers and any magnetization patterns in the magnets. This model is initially formulated according to Laplace's and Poisson's equations in 2-D polar coordinates by the separation of variables technique in four subdomains, such as magnet, airgap, winding slots, and slot-openings. The field solution of each subdomain is obtained applying the appropriate boundary conditions and interface conditions between every two subdomains, respectively, which can precisely account for the mutual influence between slots. Finite element analysis (FEA) is later deployed to validate the analytical results in a surface-mounted PM machine that has nonoverlapping winding arrangement. For validation purposes, PM machines having 3-slot/2-pole with parallel magnetization and 12-slot/10-pole with either parallel or radial magnetizations are used for comparisons. Computation of global quantities for the motor which include the phase back-EMF and cogging torque is also included. The results indicate that the proposed analytical model can accurately predict the magnetic field distributions in each subdomain and the motor's global quantities, which are in good agreement with those obtained from the FEA.

Electrochemical method for studying localized corrosion beneath disbonded coatings under cathodic protection

This paper presents a new method for measuring localized corrosion under disbonded coatings by means of an electrochemical sensor, denoted differential aeration sensor (DAS). It measures the distribution of electrochemical currents over an electrode array surface partially covered by a crevice that simulates a disbonded coating. The DAS has been evaluated using immersion tests at open circuit and under cathodic protection (CP) conditions. Under both conditions, anodic as well as cathodic current densities were detected within the crevice. A fundamental understanding for the detection of anodic currents under CP has been explained in terms of basic electrochemistry. Based on the current distribution data provided by the sensor, two different analysis methods have been used to estimate corrosion and its distribution. These methods consisted of a direct application of Faraday's Law to the anodic currents detected by the array, and on a sensor-specific method denoted corrected currents' method. It has been demonstrated that under diffusion controlled conditions this latter method produces a better corrosion estimation than the direct application of Faraday's Law. The corrected currents' method allowed the estimation of corrosion patterns outside the crevice under CP. Good correlation between electrochemical calculations and surface profilometry results has been obtained.

Evaluation of electrochemical methods for determination of the seebeck coefficient of redox electrolytes

Recent advances in thermoelectrochemical cells, which are being developed for harvesting low grade waste heat, have shown the promise of cobalt bipyridyl salts as the active redox couple. The Seebeck coefficient, Se, of a redox couple determines the open circuit voltage achievable, for a given temperature gradient, across the thermoelectrochemical cell. Thus, the accurate determination of this thermodynamic parameter is key to the development and study of new redox electrolytes. Further, techniques for accurate determination of Se using only one half of the redox couple reduces the synthetic requirements. Here, we compare three different experimental techniques for measuring Se of a cobalt tris(bipyridyl) redox couple in ionic liquid electrolytes. The use of temperature dependent cyclic voltammetry (CV) in isothermal and non-isothermal cells was investigated in depth, and the Se values compared to those from thermo-electromotive force measurements. Within experimental error, the Se values derived from CV methods were found to be in accordance with those obtained from electromotive force (emf) measurements. The applicability of cyclic voltammetry techniques for determining Se when employing only one part of the redox couple was demonstrated.

A non-fullerene electron acceptor based on central carbazole and terminal diketopyrrolopyrrole functionalities for efficient, reproducible and solution-processable bulk-heterojunction devices

A novel, solution-processable non-fullerene electron acceptor, 6,6′-((9-(heptadecan-9-yl)-9H-carbazole-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (coded as N7), based on central carbazole and terminal diketopyrrolopyrrole building blocks was designed, synthesized and characterized. N7 displayed excellent solubility, thanks to its design allowing incorporation of numerous lipophilic chains, thermal stability, and afforded a 2.30% power conversion efficiency with a high open-circuit voltage (1.17 V) when tested with the conventional donor polymer poly(3-hexylthiophene) in solution-processable bulk-heterojunction devices. To our knowledge, not only is N7 the first reported chromophore based on carbazole and diketopyrrolopyrrole functionalities but the open-circuit voltage reported here is among the highest values for a single junction bulk-heterojunction device that has been fabricated using a simple device architecture, with reproducible outcomes and with no special treatment.

Dust as an unalterable deteriorative factor affecting PV panel's efficiency: why and how

Electricity generation from solar energy has a great potential since it relies mainly on an abundant and clean source. However, there are many alterable and unalterable factors that can govern a PV module's efficiency. Dust is one of the location-dependent environmental factors that falls under the unalterable factors group. It can degrade the efficiency of a PV panel by causing physical damages, by attenuating the incoming solar radiation and by causing temperature rise, which results in changes in panel's electrical characteristics. Degree of degradation depends mainly on the deposition density, which is governed by various factors. Dust accumulation of 20 g/m2 on a PV panel reduces short circuit current, open circuit voltage and efficiency by 15–21%, 2–6% and 15–35% respectively. This work reviews, elaborates and summarizes the effects of dust on solar panel efficiency and the factors governing dust deposition on PV panel.

High thermal gradient in thermo-electrochemical cells by insertion of a poly(vinylidene fluoride) membrane

Thermo-Electrochemical cells (Thermocells/TECs) transform thermal energy into electricity by means of electrochemical potential disequilibrium between electrodes induced by a temperature gradient (ΔT). Heat conduction across the terminals of the cell is one of the primary reasons for device inefficiency. Herein, we embed Poly(Vinylidene Fluoride) (PVDF) membrane in thermocells to mitigate the heat transfer effects - we refer to these membrane-thermocells as MTECs. At a ΔT of 12 K, an improvement in the open circuit voltage (Voc) of the TEC from 1.3 mV to 2.8 mV is obtained by employment of the membrane. The PVDF membrane is employed at three different locations between the electrodes i.e. x = 2 mm, 5 mm, and 8 mm where 'x' defines the distance between the cathode and PVDF membrane. We found that the membrane position at x = 5 mm achieves the closest internal ΔT (i.e. 8.8 K) to the externally applied ΔT of 10 K and corresponding power density is 254 nWcm-2; 78% higher than the conventional TEC. Finally, a thermal resistivity model based on infrared thermography explains mass and heat transfer within the thermocells.

An open source approach for regional cortical bone mineral density analysis

Objective: Cortical porosity, particularly at the endocortical region, is recognised to play a central role in the pathogenesis of bone fragility. Therefore, the purpose of this study was to: 1) demonstrate how cortical volumetric BMD (vBMD) distribution can be analysed from (p)QCT images and 2) highlight the clinical significance of assessing regional density distribution of cortical bone. 

Methods: We used pQCT to compare mid-tibial cortical volumetric BMD distribution of 20 young (age 24(SD2) years, mass 77(11) kg, height 178(6) cm) and 25 elderly (72(4) years, 75(9) kg, 172(5) cm) men. Radial and polar cortical vBMD distributions were analysed using a custom built open source analysis tool which allowed the cortex to be divided into three concentric cortical divisions and in 36 cortical sectors originating from the centroid of the bone.

Results: Mean vBMD did not differ between the groups (1135(16) vs. 1130(28) mg/cm, P=0.696). In contrast, there was a significant age-group by radial division interaction for radial cortical vBMD (P<0.001).

Conclusions: The proposed analysis method for analysing cortical bone density distribution of pQCT images was effective for detecting regional differences in cortical density between young and elderly men, which would have been missed by just looking at mean vBMD values.

Coastal responses to estuarine discharge from intermittently open systems

This thesis is the first study to examine the interaction between estuarine discharge and coastal environments, for intermittent estuaries in Victoria. The study examined water quality, bacteria and seaweed communities and the diet of mussels, concluding that estuarine discharge is an important driver for the productivity of nearshore marine environments.

A formal model of mixed-initiative interaction in design exploration

Computer-based environments for supporting design are complex software artifacts. These tools need to use sound computational formalisms as well as address issues of human usability. The development of interactive and usable generative systems is a significant research area in design computation. Though classical search techniques play a central role in the generative kernels of these "closed-world" systems, the open-ended exploration of design spaces is the desirable goal. In this paper, we present a formal model of exploration that combines search with user driven exploration. We describe the role of interaction and agency in an experimental mixed-initiative design support system.