Recombination in Polymer:Fullerene Solar Cells with Open‐Circuit Voltages Approaching and Exceeding 1.0 V

Polymer:fullerene solar cells are demonstrated with power conversion efficiencies over 7% with blends of PBDTTPD and PC₆₁BM. These devices achieve open‐circuit voltages (V_oc) of 0.945 V and internal quantum efficiencies of 88%, making them an ideal candidate for the large bandgap junction in tandem solar cells. V_oc’s above 1.0 V are obtained when the polymer is blended with multiadduct fullerenes; however, the photocurrent and fill factor are greatly reduced. In PBDTTPD blends with multiadduct fullerene ICBA, fullerene emission is observed in the photoluminescence and electroluminescence spectra, indicating that excitons are recombining on ICBA. Voltage‐dependent, steady state and time‐resolved photoluminescence measurements indicate that energy transfer occurs from PBDTTPD to ICBA and that back hole transfer from ICBA to PBDTTPD is inefficient. By analyzing the absorption and emission spectra from fullerene and charge transfer excitons, we estimate a driving free energy of –0.14 ± 0.06 eV is required for efficient hole transfer. These results suggest that the driving force for hole transfer may be too small for efficient current generation in polymer:fullerene solar cells with V_oc values above 1.0 V and that non‐fullerene acceptor materials with large optical gaps (>1.7 eV) may be required to achieve both near unity internal quantum efficiencies and values of V_oc exceeding 1.0 V.     

Efficient,Cyanine Dye Based Bilayer Solar Cells

Simple bilayer solar cells, using commercially available cationic cyanine dyes as donors and evaporated C₆₀ layer as an acceptor are prepared. Cyanine dyes with absorption maxima of 578, 615 and 697 nm having either perchlorate or hexafluorophosphate counter‐ions are evaluated. The perchlorate dye leads to cells with S‐shape current‐voltage curves; only the dyes with the hexafluorophosphate counter‐ions lead to efficient solar cells. When the wide bandgap dyes are employed, S‐shape current‐voltage curves are obtained when the conductive polymer PEDOT:PSS is used as hole transport layer. Substitution of PEDOT:PSS with MoO₃ leads to cells with more rectangular current–voltage curves and high fill factors. Additionally, the cells using the MoO₃ layer for hole extraction lead to high open circuit voltages of 0.9 V. In the case that a low bandgap hexafluorophosphate dye is used with the HOMO above that of the PEDOT:PSS the cell performance is independent on the type of hole transport layer employed. Using this approach, bilayer solar cells are obtained with power efficiencies ranging from 1.8 to 2.9% depending on the particular dye employed. These are impressive numbers for bilayer solar cell that are partially solution processed in ambient conditions.     

The Effects of Catalyst Layer Deposition Methodology on Electrode Performance

The catalyst layer of the cathode is arguably the most critical component of low‐temperature fuel cells and carbon dioxide (CO₂) electrolysis cells because their performance is typically limited by slow oxygen (O₂) and CO₂ reduction kinetics. While significant efforts have focused on developing cathode catalysts with improved activity and stability, fewer efforts have focused on engineering the catalyst layer structure to maximize catalyst utilization and overall electrode and system performance. Here, we study the performance of cathodes for O₂ reduction and CO₂ reduction as a function of three common catalyst layer preparation methods: hand‐painting, air‐brushing, and screen‐printing. We employed ex‐situ X‐ray micro‐computed tomography (MicroCT) to visualize the catalyst layer structure and established data processing procedures to quantify catalyst uniformity. By coupling structural analysis with in‐situ electrochemical characterization, we directly correlate variation in catalyst layer morphology to electrode performance. MicroCT and SEM analyses indicate that, as expected, more uniform catalyst distribution and less particle agglomeration, lead to better performance. Most importantly, the analyses reported here allow for the observed differences over a large geometric volume as a function of preparation methods to be quantified and explained for the first time. Depositing catalyst layers via a fully‐automated air‐brushing method led to a 56% improvement in fuel cell performance and a significant reduction in electrode‐to‐electrode variability. Furthermore, air‐brushing catalyst layers for CO₂ reduction led to a 3‐fold increase in partial CO current density and enhanced product selectivity (94% CO) at similar cathode potential but a 10‐fold decrease in catalyst loading as compared to previous reports.     

Si‐Encapsulating Hollow Carbon Electrodes via Electroless Etching for Lithium‐Ion Batteries

Remarkable improvements in the electrochemical performance of Si materials for Li‐ion batteries have been recently achieved, but the inherent volume change of Si still induces electrode expansion and external cell deformation. Here, the void structure in Si‐encapsulating hollow carbons is optimized in order to minimize the volume expansion of Si‐based anodes and improve electrochemical performance. When compared to chemical etching, the hollow structure is achieved via electroless etching is more advanced due to the improved electrical contact between carbon and Si. Despite the very thick electrodes (30 ～ 40 μm), this results in better cycle and rate performances including little capacity fading over 50 cycles and 1100 mA h g^?1 at 2C rate. Also, an in situ dilatometer technique is used to perform a comprehensive study of electrode thickness change, and Si‐encapsulating hollow carbon mitigates the volume change of electrodes by adoption of void space, resulting in a small volume increase of 18% after full lithiation corresponding with a reversible capacity of about 2000 mA h g^?1.     

Schizymenia jonssonii sp. nov. (Nemastomatales,Rhodophyta): a relict or an introduction into the North Atlantic after the last glacial maximum?

North-Atlantic records of Schizymenia dubyi extend along the eastern shores of the North Atlantic from Morocco to southern Britain and Ireland, and the species is also recorded from Iceland. A study was undertaken to confirm the identity of the specimens from Iceland that were geographically separate from the main distribution of S. dubyi and in contrast to other species of the genus did not have gland cells. We analyzed rbcL and COI molecular sequence data from Icelandic specimens and compared the results with those for Schizymenia specimens available in GenBank. For both markers, Schizymenia was shown to be a monophyletic genus. The Icelandic specimens were clearly genetically distinct from S. dubyi and formed a well-supported clade with Schizymenia species from the Northern Pacific. Based on these results, we have described a new species, Schizymenia jonssonii, which can be distinguished by molecular phylogeny, its lack of gland cells and by being strictly intertidal. Crustose tetrasporophytes with identical COI and rbcL sequences were found at the same locations as foliose plants. Schizymenia apoda is reported for the first time in the UK, its identity confirmed by rbcL sequence data. In light of these findings, it is likely that by further molecular analysis of the genus Schizymenia in the north-eastern Atlantic and the Mediterranean, a higher diversity of Schizymenia spp. will be discovered in this region.     

Continental estimates of forest cover and forest cover changes in the dry ecosystems of Africa between 1990 and 2000

Aim

This study provides regional estimates of forest cover in dry African ecoregions and the changes in forest cover that occurred there between 1990 and 2000, using a systematic sample of medium‐resolution satellite imagery which was processed consistently across the continent.

Location

The study area corresponds to the dry forests and woodlands of Africa between the humid forests and the semi‐arid regions. This area covers the Sudanian and Zambezian ecoregions.

Methods

A systematic sample of 1600 Landsat satellite imagery subsets, each 20 km × 20 km in size, were analysed for two reference years: 1990 and 2000. At each sample site and for both years, dense tree cover, open tree cover, other wooded land and other vegetation cover were identified from the analysis of satellite imagery, which comprised multidate segmentation and automatic classification steps followed by visual control by national forestry experts.

Results

Land cover and land‐cover changes were estimated at continental and ecoregion scales and compared with existing pan‐continental, regional and local studies. The overall accuracy of our land‐cover maps was estimated at 87%. Between 1990 and 2000, 3.3 million hectares (Mha) of dense tree cover, 5.8 Mha of open tree cover and 8.9 Mha of other wooded land were lost, with a further 3.9 Mha degraded from dense to open tree cover. These results are substantially lower than the 34 Mha of forest loss reported in the FAO's 2010 Global Forest Resources Assessment for the same period and area.

Main conclusions

Our method generates the first consistent and robust estimates of forest cover and change in dry Africa with known statistical precision at continental and ecoregion scales. These results reduce the uncertainty regarding vegetation cover and its dynamics in these previously poorly studied ecosystems and provide crucial information for both science and environmental policies.