Analysis of dye degradation products and assessment of the dye purity in dye-sensitized solar cells.

RATIONALE: For commercialization of dye-sensitized solar cells (DSSCs), improvement of their long-term stability and efficiency is important. A key component in solar cells is the dye, its high purity and high stability. Here, methods for dye extraction and purification, and for determination of dye purity and dye degradation in DSSCs, were developed. METHODS: A method was developed for extraction of the dye Z907 from intact solar cells using a water/ethanol mixture containing tetrabutylammonium hydroxide. The N719 dye synthesized in our laboratory was purified by gel filtration on Sephadex LH20. These dyes, along with the dyes N3 and RuL2 (NC)2, were analyzed using nuclear magnetic resonance (NMR) spectroscopy and liquid chromatography coupled to an electrospray ionization quadrupole-time-of-flight mass analyzer (LC/MS) operating in negative ionization mode. RESULTS: Purification of the synthesized N719 removed several impurities, including its undesired isomer with the thiocyanate ligand attached to ruthenium through sulfur instead of nitrogen. The dyes N719 and Z907 were successfully extracted from solar cells and together with N3 and RuL2 (NC)2 analyzed by LC/MS, although N719 isomerized almost immediately in basic aqueous solution. The [M-H](-1) ions were observed and the measured mass was within a ±6 ppm range from the exact mass. CONCLUSIONS: LC/MS in combination with NMR spectroscopy was shown to provide useful information on dye structure, purity, and on the efficiency of the purification methods. These methods allow for further studies of solar cell dyes, which may provide the detailed information needed for the improvement and eventual commercialization of the solar cell technology.

Effect of electrolyte bleaching on the stability and performance of dye solar cells.

Degradation of dye solar cells (DSCs) under severe ageing conditions may lead to loss of the tri-iodide in the electrolyte - a phenomenon known as electrolyte bleaching. Monitoring changes in the tri-iodide concentration as a result of degradation mechanisms and understanding their causes and effects are fundamental for improving the long-term stability of DSCs. In this contribution a strongly accelerated ageing test (1 Sun visible light, 1.5 Suns UV light, T = 110 °C for 12 h) was performed on DSCs in a double-sealed masterplate configuration to purposely induce severe electrolyte bleaching, and its effects on the performance and stability of DSCs with different initial tri-iodide concentrations [I3(-)]0 were investigated. The cells with low [I3(-)]0 suffered a severe loss in short circuit current density JSC (up to 85%). Also a significant loss of open circuit voltage VOC was observed and this loss was proportional to [I3(-)]0 with the highest VOC drop observed with the highest [I3(-)]0. Non-destructive analysis techniques based on the limited current density, JSCvs. light intensity, and photographic image analysis, were used to quantify the [I3(-)] loss, which was found to be ca. 50 mM and independent of [I3(-)]0. Quantitative model based VOC analysis in terms of changing [I3(-)] revealed that the degradation responsible for the VOC drop was dominated by an unknown mechanism that is unrelated to [I3(-)]0. The methods and results reported here help separating and identifying different degradation mechanisms related to electrolyte bleaching in DSCs.

Processing factors affecting roughness, optical and mechanical properties of nanocellulose films for optoelectronics.

This work aims to understand how nanocellulose (NC) processing can modify the key characteristics of NC films to align with the main requirements for high-performance optoelectronics. The performance of these devices relies heavily on the light transmittance of the substrate, which serves as a mechanical support and optimizes light interactions with the photoactive component. Critical variables that determine the optical and mechanical properties of the films include the morphology of cellulose nanofibrils (CNF), as well as the concentration and turbidity of the respective aqueous suspensions. This study demonstrates that achieving high transparency was possible by reducing the grammage and adjusting the drying temperature through hot pressing. Furthermore, the use of modified CNF, specifically carboxylated CNF, resulted in more transparent films due to a higher nanosized fraction and lower turbidity. The mechanical properties of the films depended on their structure, homogeneity (spatial uniformity of local grammage), and electrokinetic factors, such as the presence of electrostatic charges on CNF. Additionally, we investigated the angle-dependent transmittance of the CNF films, since solar devices usually operate under indirect light. This work demonstrates the importance of a systematic approach to the optimization of cellulose films, providing valuable insight into the optoelectronic field.

Eco-design for perovskite solar cells to address future waste challenges and recover valuable materials.

Photovoltaic development should be steered by the circular economy. However, it is not. In case of perovskite photovoltaics even current environmental directives divert from profitably recycling. Here, we study the profitability of noble metals recovery from wasted perovskite solar cells depending on recycling routes. Our results show that substrates play a major role in the recovery of precious metals and in contrast to previous research even recycling carbon-based devices could reach profitability. Going beyond the recovery of valuable elements, our findings show that revival of the perovskite solar cells is strongly dependent on the device architecture, so far viable for mesoscopic structures with carbon back contacts. Perovskite solar cells are still at the development stage, but the window of opportunity to ensure eco-design will close with market entry, and device complexity might compromise profitability recycling and even result in failure of recovery critical materials. Therefore, its eco-design should be prioritized by materials researchers to develop devices, where valuable components can be separated and liberated with safe and low energy processes.

Isolation of Mixed Compositions of Cellulose Nanocrystals, Microcrystalline Cellulose, and Lignin Nanoparticles from Wood Pulps.

From a circular economy perspective, one-pot strategies for the isolation of cellulose nanomaterials at a high yield and with multifunctional properties are attractive. Here, the effects of lignin content (bleached vs unbleached softwood kraft pulp) and sulfuric acid concentration on the properties of crystalline lignocellulose isolates and their films are explored. Hydrolysis at 58 wt % sulfuric acid resulted in both cellulose nanocrystals (CNCs) and microcrystalline cellulose at a relatively high yield (>55%), whereas hydrolysis at 64 wt % gave CNCs at a lower yield (<20%). CNCs from 58 wt % hydrolysis were more polydisperse and had a higher average aspect ratio (1.5-2×), a lower surface charge (2×), and a higher shear viscosity (100-1000×). Hydrolysis of unbleached pulp additionally yielded spherical nanoparticles (NPs) that were <50 nm in diameter and identified as lignin by nanoscale Fourier transform infrared spectroscopy and IR imaging. Chiral nematic self-organization was observed in films from CNCs isolated at 64 wt % but not from the more heterogeneous CNC qualities produced at 58 wt %. All films degraded to some extent under simulated sunlight trials, but these effects were less pronounced in lignin-NP-containing films, suggesting a protective feature, but the hemicellulose content and CNC crystallinity may be implicated as well. Finally, heterogeneous CNC compositions obtained at a high yield and with improved resource efficiency are suggested for specific nanocellulose uses, for instance, as thickeners or reinforcing fillers, representing a step toward the development of application-tailored CNC grades.

Plant-Based Structures as an Opportunity to Engineer Optical Functions in Next-Generation Light Management.

This review addresses the reconstruction of structural plant components (cellulose, lignin, and hemicelluloses) into materials displaying advanced optical properties. The strategies to isolate the main building blocks are discussed, and the effects of fibrillation, fibril alignment, densification, self-assembly, surface-patterning, and compositing are presented considering their role in engineering optical performance. Then, key elements that enable lignocellulosic to be translated into materials that present optical functionality, such as transparency, haze, reflectance, UV-blocking, luminescence, and structural colors, are described. Mapping the optical landscape that is accessible from lignocellulosics is shown as an essential step toward their utilization in smart devices. Advanced materials built from sustainable resources, including those obtained from industrial or agricultural side streams, demonstrate enormous promise in optoelectronics due to their potentially lower cost, while meeting or even exceeding current demands in performance. The requirements are summarized for the production and application of plant-based optically functional materials in different smart material applications and the review is concluded with a perspective about this active field of knowledge.

Thin film nano solar cells--from device optimization to upscaling.

Stainless steel based dye solar cells have been upscaled from small, laboratory size test cells of 0.32 cm2 active area to 6 cm x 6 cm "mini-modules" with active areas ca. 15 cm2. Stainless steel works as the photoelectrode substrate whilst the counter electrode is prepared on indium-doped tin oxide coated polyethyleneterephtalate or polyethylenenaphtalate plastic foil (fluorine-doped tin oxide coated glass as a reference). Additional current collector structures were deposited on the counter electrode substrate with inkjet-printing of silver nanoparticle ink in order to reduce the lateral resistance of the plastic foil. Flexible substrates enable roll-to-roll type industrial manufacturing of the cells and the steel's superior conductivity compared to the typical substrate materials such as glass and plastic makes it possible to prepare even substantially larger modules. The best efficiencies obtained this far with the "mini-module" using a stainless steel photoelectrode are 2.5% with a platinum-sputtered indium-doped tin oxide coated polyethyleneterephtalate counter electrode and 3.4% with a thermally platinized fluorine-doped tin oxide coated glass counter electrode. These efficiencies are on the same level than those measured with small cells prepared with similar methods and materials (3.4%-4.7%, depending on configuration, which are amongst the highest reported for this kind of a dye solar cell). Replacing expensive conducting glass with steel and plastic foils as the substrate materials leads also to economical savings in the cell production.

Cellulose Nanocrystal Aerogels as Electrolyte Scaffolds for Glass and Plastic Dye-Sensitized Solar Cells.

The fabrication, thickness, and structure of aerogel films composed of covalently cross-linked cellulose nanocrystals (CNCs) and poly(oligoethylene glycol methacrylate) (POEGMA) were optimized for use as electrolyte absorbers in dye-sensitized solar cells (DSSCs). The aerogel films were cast directly on transparent conducting counter electrode substrates (glass and flexible poly(ethylene terephthalate) plastic) and then used to absorb drop-cast liquid electrolyte, thus providing an alternative method of filling electrolyte in DSSCs. This approach eliminates the use of electrolyte-filling holes, which are a typical pathway of electrolyte leakage, and furthermore enables a homogeneous distribution of electrolyte components within the photoelectrode. Unlike typical in situ electrolyte gelation approaches, the phase inversion method used here results in a highly porous (>99%) electrolyte scaffold with excellent ionic conductivity and interfacial properties. DSSCs prepared with CNC-POEGMA aerogels reached similar power conversion efficiencies as compared to liquid electrolyte devices, indicating that the aerogel does not interfere with the operation of the device. These aerogels retain their structural integrity upon bending, which is critical for their application in flexible devices. Furthermore, the aerogels demonstrate impressive chemical and mechanical stability in typical electrolyte solvents because of their stable covalent cross-linking. Overall, this work demonstrates that the DSSC fabrication process can be simplified and made more easily upscalable by taking advantage of CNCs, being an abundant and sustainable bio-based material.

Gel Electrolytes with Polyamidopyridine Dendron Modified Talc for Dye-Sensitized Solar Cells.

Organic-inorganic hybrid layered materials are proposed as additives in a quasi-solid gel electrolyte for dye-sensitized solar cells. Talcs could provide a low-cost and environmentally friendly, as well as abundant, option as gelators. Here, talcs were prepared by functionalizing an organotalc with three polyamidopyridine dendron generations, PAMPy-talc-Gn (n = 1, 2 and 3). PAMPy dendrons grow parallel to the lamellae plane and form an organized structure by intermolecular interactions. In addition, polyiodide-dendron charge-transfer complexes were prepared onto the organotalc by adsorption of iodine. In this work, the effect of the dendron generation of PAMPy-talc and the influence of polyiodide intercalation on solar cell performance and stability were investigated. The best results were reached with the use of lowest-generation PAMPy-talc (η = 4.5 ± 0.3%, VOC = 710 ± 19 mV, Jsc = 10.4 ± 0.9 mA cm-2, and FF = 61 ± 2%): 15% higher efficiency compared to similar liquid devices. While some previously studied talcs illustrate very strong absorption of the iodide from the electrolyte, in the case of PAMPy-talc such interfering effects were absent: In a 1000 h light soaking test, the PAMPy-talc cells both with and without polyiodide intercalation demonstrated stable performances. Furthermore, the color analysis of the electrolyte indicated that the color of the electrolyte remained stable after an initial period of stabilization, which is a good indication of the compound being stable and not absorbing charge carriers from the electrolyte. The performance and stability results indicate that PAMPy-talc has potential as a gelling method for electrolytes for dye solar cells.

Interpretation of optoelectronic transient and charge extraction measurements in dye-sensitized solar cells.

Tools that assess the limitations of dye sensitized solar cells (DSSCs) made with new materials are critical for progress. Measuring the transient electrical signals (voltage or current) after optically perturbing a DSSC is an approach which can give information about electron concentration, transport and recombination. Here we describe the theory and practice of this class of optoelectronic measurements, illustrated with numerous examples. The measurements are interpreted with the multiple trapping continuum model which describes electrons in a semiconductor with an exponential distribution of trapping states. We review standard small perturbation photocurrent and photovoltage transients, and introduce the photovoltage time of flight measurement which allows the simultaneous derivation of both effective diffusion and recombination coefficients. We then consider the utility of large perturbation measurements such as charge extraction and the current interrupt technique for finding the internal charge and voltage within a device. Combining these measurements allows differences between DSSCs to be understood in terms such as electron collection efficiency, semiconductor conduction band edge shifts and recombination kinetics.

Device physics of dye solar cells.

Design of new materials for nanostructured dye solar cells (DSC) requires understanding the link between the material properties and cell efficiency. This paper gives an overview of the fundamental and practical aspects of the modeling and characterization of DSCs, and integrates the knowledge into a user-friendly DSC device model. Starting from basic physical and electrochemical concepts, mathematical expressions for the IV curve and differential resistance of all resistive cell components are derived and their relation to electrochemical impedance spectroscopy (EIS) is explained. The current understanding of the associated physics is discussed in detail and clarified. It is shown how the model parameters can be determined from complete DSCs by current dependent EIS and incident-photon-to-collected-electron (IPCE) measurements, supplemented by optical characterization, and used to quantify performance losses in DSCs. The paper aims to give a necessary theoretical background and practical guidelines for establishing an effective feedback-loop for DSC testing and development.