The possibility of achieving many electrons per absorbed photon of sufficient energy by quantum dots (QDs) drives the motivation to build high performance quantum dot solar cells (QDSCs). Although performance of dye-sensitized solar cells (DSCs), with similar device configuration as that of QDSCs, has significantly improved in the last two decades QDSCs are yet to demonstrate impressive device performances despite the remarkable features of QDs as light harvesters. We investigated the fundamental differences in the optical properties of QDs and dyes using DFT calculations to get insights on the inferior performance of QDSCs. The CdSe QDs and the ruthenium bipyridyl dicarboxylic acid dye (N3) were used as typical examples in this study. Based on a generalized equation of state correlating material properties and photoconversion efficiency, we calculated ground and excited state properties of these absorbers at the B3LYP/lanl2dz level of DFT and analyzed them on the basis of the device performance. Five missing links have been identified in the study which provides numerous insights into building high efficiency QDSCs. They are (i) fundamental differences in the emitting states of the QDs in the strong and weak confinement regimes were observed, which explained successfully the performance differences; (ii) the crucial role of bifunctional ligands that bind the QDs and the photo-electrode was identified; in most cases use of bifunctional ligands does not lead to a QD enabled widening of the absorption of the photo-electrode; (iii) wide QDs size distribution further hinders efficient electron injections; (iv) wide absorption cross-section of QDs favours photon harvesting; and (v) the role of redox potential of the electrolyte in the QD reduction process.
Despite the high efficiency of over 21% reported for emerging thin film perovskite solar cells, one of the key issues prior to their commercial deployment is to attain their long term stability under ambient and outdoor conditions. The instability in perovskite is widely conceived to be humidity induced due to the water solubility of its initial precursors, which leads to decomposition of the perovskite crystal structure; however, we note that humidity alone is not the major degradation factor and it is rather the photon dose in combination with humidity exposure that triggers the instability. In our experiment, which is designed to decouple the effect of humidity and light on perovskite degradation, we investigate the shelf-lifetime of CH3NH3PbI3 films in the dark and under illumination under high humidity conditions (Rel. H. > 70%). We note minor degradation in perovskite films stored in a humid dark environment whereas upon exposure to light, the films undergo drastic degradation, primarily owing to the reactive TiO2/perovskite interface and also the surface defects of TiO2. To enhance its air-stability, we incorporate CH3NH3PbI3 perovskite in a polymer (poly-vinylpyrrolidone, PVP) matrix which retained its optical and structural characteristics in the dark for ∼2000 h and ∼800 h in room light soaking, significantly higher than a pristine perovskite film, which degraded completely in 600 h in the dark and in less than 100 h when exposed to light. We attribute the superior stability of PVP incorporated perovskite films to the improved structural stability of CH3NH3PbI3 and also to the improved TiO2/perovskite interface upon incorporating a polymer matrix. Charge injection from the polymer embedded perovskite films has also been confirmed by fabricating solar cells using them, thereby providing a promising future research pathway for stable and efficient perovskite solar cells.
This article addresses the heat capacity of quantum dots (QDs) using density functional theory (DFT). By analyzing the evolution of phonon density of states and heat capacity as CdSe clusters grow from a molecular cluster into larger quantum confined solids, we have shown that their heat capacity does not fit very well with the Debye T3 model. We observed that the number of phonon modes, which is discrete, increases as the particles grow, and the dispersion relation shows a quadratic behavior in contrast to the bulk solids whose dispersion relation is linear and equal to the sound velocity. The phonon density of states showed a square root variation with respect to frequency whereas that of the bulk is a quadratic variation of frequency. From the observed variation in the phonon density of states and holding the fact that the atomic vibrations in solids are elastically coupled, we have re-derived the expression for total energy of the QDs and arrive at a T3/2 model of heat capacity, which fits very well to the observed heat capacity data. These results give promising directions in the understanding of the evolution of the thermophysical properties of solids.
In this report, a facile solution casting technique was used to fabricate polymer blend electrolytes of chitosan (CS):poly (ethylene oxide) (PEO):NH4SCN with high electrochemical stability (2.43V). Fourier transform infrared (FTIR) spectroscopy was used to investigate the polymer electrolyte formation. For the electrochemical property analysis, cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) techniques were carried out. Referring to the FTIR spectra, a complex formation between the added salt and CS:PEO was deduced by considering the decreasing and shifting of FTIR bands intensity in terms of functional groups. The CS:PEO:NH4SCN electrolyte was found to be electrochemically stable as the applied voltage linearly swept up to 2.43V. The cyclic voltammogram has presented a wide potential window without showing any sign of redox peaks on the electrode surface. The proved mechanisms of charge storage in these fabricated systems were found to be double layer charging. The EIS analysis showed the existence of bulk resistance, wherein the semicircle diameter decreased with increasing salt concentration. The calculated maximum DC conductivity value was observed to be 2.11 × 10-4 S/cm for CS:PEO incorporated with 40 wt% of NH4SCN salt. The charged species in CS:PEO:NH4SCN electrolytes were considered to be predominantly ionic in nature. This was verified from transference number analysis (TNM), in which ion and electron transference numbers were found to be tion = 0.954 and tel = 0.045, respectively. The results obtained for both ion transference number and DC conductivity implied the possibility of fabricating electrolytes for electrochemical double layer capacitor (EDLC) device application. The specific capacitance of the fabricated EDLC was obtained from the area under the curve of the CV plot.
Chitosan (CS)-dextran (DN) biopolymer electrolytes doped with ammonium iodide (NH4I) and plasticized with glycerol (GL), then dispersed with Zn(II)-metal complex were fabricated for energy device application. The CS:DN:NH4I:Zn(II)-complex was plasticized with various amounts of GL and the impact of used metal complex and GL on the properties of the formed electrolyte were investigated.The electrochemical impedance spectroscopy (EIS) measurements have shown that the highest conductivity for the plasticized system was 3.44 × 10-4 S/cm. From the x-ray diffraction (XRD) measurements, the plasticized electrolyte with minimum degree of crystallinity has shown the maximum conductivity. The effect of (GL) plasticizer on the film morphology was studied using FESEM. It has been confirmed via transference number analysis (TNM) that the transport mechanism in the prepared electrolyte is predominantly ionic in nature with a high transference number of ion (ti)of 0.983. From a linear sweep voltammetry (LSV) study, the electrolyte was found to be electrochemically constant as the voltage sweeps linearly up to 1.25 V. The cyclic voltammetry (CV) curve covered most of the area of the current-potential plot with no redox peaks and the sweep rate was found to be affecting the capacitance. The electric double-layer capacitor (EDLC) has shown a great performance of specific capacitance (108.3 F/g), ESR(47.8 ohm), energy density (12.2 W/kg) and power density (1743.4 W/kg) for complete 100 cycles at a current density of 0.5 mA cm-2.
In this study, the solution casting method was employed to prepare plasticized polymer electrolytes of chitosan (CS):LiCO2CH3:Glycerol with electrochemical stability (1.8 V). The electrolyte studied in this current work could be established as new materials in the fabrication of EDLC with high specific capacitance and energy density. The system with high dielectric constant was also associated with high DC conductivity (5.19 × 10-4 S/cm). The increase of the amorphous phase upon the addition of glycerol was observed from XRD results. The main charge carrier in the polymer electrolyte was ion as tel (0.044) < tion (0.956). Cyclic voltammetry presented an almost rectangular plot with the absence of a Faradaic peak. Specific capacitance was found to be dependent on the scan rate used. The efficiency of the EDLC was observed to remain constant at 98.8% to 99.5% up to 700 cycles, portraying an excellent cyclability. High values of specific capacitance, energy density, and power density were achieved, such as 132.8 F/g, 18.4 Wh/kg, and 2591 W/kg, respectively. The low equivalent series resistance (ESR) indicated that the EDLC possessed good electrolyte/electrode contact. It was discovered that the power density of the EDLC was affected by ESR.
In this study, biopolymer composite electrolytes based on chitosan:ammonium iodide:Zn(II)-complex plasticized with glycerol were successfully prepared using the solution casting technique. Various electrical and electrochemical parameters of the biopolymer composite electrolytes' films were evaluated prior to device application. The highest conducting plasticized membrane was found to have a conductivity of 1.17 × 10-4 S/cm. It is shown that the number density, mobility, and diffusion coefficient of cations and anions fractions are increased with the glycerol amount. Field emission scanning electron microscope and Fourier transform infrared spectroscopy techniques are used to study the morphology and structure of the films. The non-Debye type of relaxation process was confirmed from the peak appearance of the dielectric relaxation study. The obtained transference number of ions (cations and anions) and electrons for the highest conducting sample were identified to be 0.98 and 0.02, respectively. Linear sweep voltammetry shows that the electrochemical stability of the highest conducting plasticized system is 1.37 V. The cyclic voltammetry response displayed no redox reaction peaks over its entire potential range. It was discovered that the addition of Zn(II)-complex and glycerol plasticizer improved the electric double-layer capacitor device performances. Numerous crucial parameters of the electric double-layer capacitor device were obtained from the charge-discharge profile. The prepared electric double-layer capacitor device showed that the initial values of specific capacitance, equivalence series resistance, energy density, and power density are 36 F/g, 177 Ω, 4.1 Wh/kg, and 480 W/kg, respectively.