Transition from Diffusion‐Controlled Intercalation into Extrinsically Pseudocapacitive Charge Storage of MoS2 by Nanoscale Heterostructuring

2D nanomaterials have been found to show surface‐dominant phenomena and understanding this behavior is crucial for establishing a relationship between a material's structure and its properties. Here, the transition of molybdenum disulfide (MoS₂) from a diffusion‐controlled intercalation to an emergent surface redox capacitive behavior is demonstrated. The ultrafast pseudocapacitive behavior of MoS₂ becomes more prominent when the layered MoS₂ is downscaled into nanometric sheets and hybridized with reduced graphene oxide (RGO). This extrinsic behavior of the 2D hybrid is promoted by the fast Faradaic charge‐transfer kinetics at the interface. The heterostructure of the 2D hybrid, as observed via high‐angle annular dark field–scanning transmission electron microscopy and Raman mapping, with a 1T MoS₂ phase at the interface and a 2H phase in the bulk is associated with the synergizing capacitive performance. This 1T phase is stabilized by the interactions with the RGO. These results provide fundamental insights into the surface effects of 2D hetero‐nanosheets on emergent electrochemical properties.     

Stable Li–Organic Batteries with Nafion‐Based Sandwich‐Type Separators

Similar to Li–S batteries, Li–organic batteries have also been plagued by the dissolution of active materials and the resulting shuttle effect for many years. An effective strategy to eliminate the shuttle effect is adopting solid electrolytes or Li–ion permselective separators to prohibit the dissolved electroactive species from migrating to the Li anode. A polypropylene/Nafion/polypropylene (PNP) sandwich‐type separator is reported with many advantages in comparison with previously reported LISICON, polymer electrolyte, and other Nafion utilization forms. The physical and chemical properties of PNP separators are studied in detail by cross‐section scanning electron microscopy (SEM), infrared spectroscopy (IR), and electrochemical impedance spectroscopy. 1,1′‐Iminodianthraquinone (IDAQ), a novel organic cathode, is taken as an example to quantitatively investigate the function of PNP separators. In the presence of PNP5 with the most appropriate Nafion loading of 0.5 mg cm^–2, IDAQ is able to achieve dramatically improved cycling stability with capacity retention of 76% after 400 cycles and Coulombic efficiency above 99.6%, which reaches the highest level for reported soluble organic electrode materials. Besides Li–organic batteries, such kind of Nafion‐based sandwich‐type separators are also promising for Li–S batteries and other new battery designs involving dissolved electroactive species.     

Nanoscale Elastic Changes in 2D Ti3C2Tx (MXene) Pseudocapacitive Electrodes

Designing sustainable electrodes for next generation energy storage devices relies on the understanding of their fundamental properties at the nanoscale, including the comprehension of ions insertion into the electrode and their interactions with the active material. One consequence of ion storage is the change in the electrode volume resulting in mechanical strain and stress that can strongly affect the cycle life. Therefore, it is important to understand the changes of dimensions and mechanical properties occurring during electrochemical reactions. While the characterization of mechanical properties via macroscopic measurements is well documented, in situ characterization of their evolution has never been achieved at the nanoscale. It is reported here with in situ imaging, combined with density functional theory of the elastic changes of a 2D titanium carbide (Ti₃C₂T_x) based electrode in direction normal to the basal plane (electrode surface) during alkaline cation intercalation/extraction. 2D carbides, known as MXenes, are promising new materials for supercapacitors and various kinds of batteries, and understanding the coupling between their mechanical and electrochemical properties is therefore necessary. The results show a strong correlation between the cations content and the out‐of‐plane elastic modulus. This strategy enables identifying the preferential intercalation pathways within a single particle, which is important for understanding ionic transport in these materials.     

Two‐Dimensional Materials for Beyond‐Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) have dominated the portable electronics industry and solid‐state electrochemical research and development for the past two decades. In light of possible concerns over the cost and future availability of lithium, sodium‐ion batteries (SIBs) and other new technologies have emerged as candidates for large‐scale stationary energy storage. Research in these technologies has increased dramatically with a focus on the development of new materials for both the positive and negative electrodes that can enhance the cycling stability, rate capability, and energy density. Two‐dimensional (2D) materials are showing promise for many energy‐related applications and particularly for energy storage, because of the efficient ion transport between the layers and the large surface areas available for improved ion adsorption and faster surface redox reactions. Recent research highlights on the use of 2D materials in these future ‘beyond‐lithium‐ion’ battery systems are reviewed, and strategies to address challenges are discussed as well as their prospects.     

Chloroperoxidase production by Caldariomyces fumago biofilms

Chloroperoxidase (CPO) is a versatile enzyme, which is secreted by the marine fungus Caldariomyces fumago (Leptoxyphium fumago). However, the application of the enzyme is hampered by its high price, which is due to the costly, labor‐intensive purification process. One challenge of the downstream process is the removal of a coproduced black pigment that forms a complex with the active enzyme. While strain development can be considered as an option to reduce the synthesis of the interfering pigment, the metabolism of the microorganism can be altered alternatively by using the biofilm growth mode of the fungus. The aim of this study was to reduce pigment formation during CPO synthesis. We investigated for the first time CPO production during C. fumago biofilm growth initiated through the presence of different microstructured stainless steel surfaces (material number: 1.4571; AISI 316Ti). CPO production by C. fumago was similar when grown as a biofilm or in suspension, whereas pigment formation was drastically reduced by cells grown on moderately structured surfaces (R_a = 0.13 ± 0.02 μm). The possibilities of biofilm growth for changing cell properties and for continuous fermentation are discussed.     

Menez-Dregan 1 (Plouhinec,Finistère,France) : un site d’habitat du Paléolithique inférieur en grotte marine. Stratigraphie,structures de combustion,industries riches en galets aménagés

The Lower Palaeolithic site of Menez-Dregan I is currently the subject of an important excavation and has been part of a multidisciplinary project since 1991. It is an ancient marine cave whose roof has gradually collapsed and thus partly protected the site from erosion. In Menez-Dregan 1, the sedimentological evidence has been significantly reduced due to multiple episodes of marine erosion in the cave (low sedimentary preservation in terms of sedimentation and erosion process). However, the proximity of a section with a longer sedimentary record (Gwendrez cliff) has allowed for an attempt at correlation between the different deposits by way of a sedimentologic study applied to sandy marker beds (dunes). The resulting new data permitted a more precise chronostratigraphy of this site to be drawn up and contributed to further validation of dating. Three main stratigraphic units show distinct levels of human occupation at the site, separated by coastal deposits. The ESR dates tend to place the first human occupation in MIS 12 or at the end of MIS 13 (around 465,000 years). The ESR dating obtained at the base of layer 5 gave an age of 380,000 years. The geological analysis (sedimentology, stratigraphical correlations at short distance) tends to confirm these dates. The fauna has not preserved due to the acidic environment, leaving only the lithic industry to show how the human groups who settled at the site lived and, it is worth noting, mastered fire lighting, and or control, at a very early date (late MIS 13 or early MIS 12). The lithic industry from the upper levels (layer 5) is likely Colombanian and is composed of numerous flakes and cores alongside a great quantity of cobble tools (mostly choppers), fractured cobbles, and cobbles with isolated removals on various types of rocks, some cleavers and very rare bifaces. Additionally denticulates and notches form the main part of the light duty tools, together with scrapers. These retouched light duty tools are mainly made on flint, but quartz and glossy sandstone were also used. The last level of occupation (layer 4) probably shows the transition between Lower and Middle Palaeolithic. This may represent a regional cobble tool industry of the south armorican shoreline, however, it is still difficult to separate it totally from the classic European Acheulean from Northern France. These armorican lithic industries could indeed correspond with areas of specialised activities, as demonstrated for some Middle Palaeolithic groups with a cobble tools lithic industry. The notion of culture that could be chosen to explain this variability must be treated with caution, because it would only be based on the presence or absence of only one type of tool (the handaxe).