Energie-Materialien

Hexacyanometallates, known as Prussian blue (PB) and its analogues (PBAs), are a class of coordination
compounds with a regular and porous open structure. The PBAs are formed by the self-assembly of
metallic species and cyanide groups. A uniform distribution of each element makes the PBAs robust
templates to prepare hollow and highly porous (hetero)nanostructures of metal oxides, sulfides, carbides,
nitrides, phosphides, and (N-doped) carbon, among other compositions. In this review, we examine
methods to derive materials from PBAs focusing on the correlation between synthesis steps and
derivative morphologies and composition. Insights into catalytic and electrochemical properties resulting
from different derivatization strategies are also presented. We discuss challenges in manipulating the
derivatives' properties, give perspectives of synthetic approaches for the target applications and present
an outlook on less investigated grounds in Prussian blue derivatives

MBenes are post-MXene materials that contain boron in their structure instead of carbon and nitrogen. This unique composition offers an opportunity to explore the role of boron in the performance of 2D materials. However, wet-chemical etching and delamination of the starting MoAlB phase are challenging due to the persistent bonding of aluminum atoms with their neighboring elements. Herein, it is overcome by processing MoAlB for 24, 48, and 72 h with an aqueous HCl/H2O2 solution. The time-wise etching and delamination delivers individual single-to-few layered 48-MBene flakes. The theoretical-to-experimental XRD analysis revealed the best-delaminated 48-MBene having Mo2B2 orthorhombic lattice arrangement. The presence of Mo oxide allows direct 1.2 eV and indirect 0.2 eV optical band gaps and outstanding photocatalytic activity in decomposing methylene blue as a model organic contaminant. The 48-MBene photocatalyst achieves about 90% of MB decomposition under ultraviolet and simulated white light irradiation with three times faster kinetics outperforming even hybridized MXenes. In addition, 48-MBene appeared best suited to utilize the full spectrum of visible light into reactive oxygen species. Conversely, 24-MBene and 72-MBene shows incomplete delamination or oxidation, hampering their photocatalytic activity. The obtained results open an experimental pathway to apply MBenes in environmental remediation.

Developing new flexible and electroactive materials is a significant challenge to producing safe, reliable, and environmentally friendly energy storage devices. This study introduces a promising electrolyte system that fulfills these requirements. First, polypyrrole (PPy) nanotubes are electropolymerized in graphite-thread electrodes using methyl orange (MO) templates in an acidic medium. The modification increases the conductivity and does not compromise the flexibility of the electrodes. Next, flexible supercapacitors are built using hydrogel prepared from poly(vinyl alcohol) (PVA)/sodium alginate (SA) obtained by freeze–thawing and swollen with ionic solutions as an electrolyte. The material exhibits a homogenous and porous hydrogel matrix allowing a high conductivity of 3.6 mS cm−1 as-prepared while displaying great versatility, changing its electrochemical and mechanical properties depending on the swollen electrolyte. Therefore, it allows its combination with modified graphite-thread electrodes into a quasi-solid electrochemical energy storage device, achieving a specific capacitance (Cs) value of 66 F g−1 at 0.5 A g−1. Finally, the flexible device exhibits specific energy and power values of 19.9 W kg−1 and 3.0 Wh kg−1, relying on the liquid phase in the hydrogel matrix produced from biodegradable polymers. This study shows an environment friendly, flexible, and tunable quasi-solid electrolyte, depending on a simple swell experiment to shape its properties according to its application.

Supercapacitors are fast-charging energy storage devices of great importance for developing robust and climate-friendly energy infrastructures for the future. Research in this field has seen rapid growth in recent years, therefore consistent reporting practices must be implemented to enable reliable comparison of device performance. Although several studies have highlighted the best practices for analysing and reporting data from such energy storage devices, there is yet to be an empirical study investigating whether researchers in the field are correctly implementing these recommendations, and which assesses the variation in reporting between different laboratories. Here we address this deficit by carrying out the first interlaboratory study of the analysis of supercapacitor electrochemistry data. We find that the use of incorrect formulae and researchers having different interpretations of key terminologies are major causes of variability in data reporting. Furthermore we highlight the more significant variation in reported results for electrochemical profiles showing non-ideal capacitive behaviour. From the insights gained through this study, we make additional recommendations to the community to help ensure consistent reporting of performance metrics moving forward.

Herein, we report the synthesis of TiO2–SnO2–C/carbide hybrid electrode materials for Li-ion batteries (LIBs) via two different methods of controlled oxidation of layered Ti2SnC. The material was partially oxidized in an open-air furnace (OAF) or using a rapid thermal annealing (RTA) approach to obtain the desired TiO2–SnO2–C/carbide hybrid material; the carbide phase encompassed both residual Ti2SnC and TiC as a reaction product. We tested the oxidized materials as an anode in a half cell to investigate their electrochemical performance in LIBs. Analysis of the various oxidation conditions indicated the highest initial lithiation capacity of 838 mAh/g at 100 mA/g for the sample oxidized in the OAF at 700°C for 1 h. Still, the delithiation capacity dropped to 427 mAh/g and faded over cycling. Long-term cycling demonstrated that the RTA sample treated at 800°C for 30 s was the most efficient, as it demonstrated a reversible capacity of around 270 mAh/g after 150 cycles, as well as a specific capacity of about 150 mAh/g under high cycling rate (2000 mA/g). Given the materials’ promising performance, this processing method could likely be applied to many other members of the MAX family, with a wide range of energy storage applications.

The fast growth of electric vehicles and electronic devices produces a mounting number of spent batteries which have reached their end of life. Therefore, it is essential to find a sustainable and efficient approach to battery recycling. Conventional recycling via high-temperature decomposition of the active components in the electrode material into elements level has the disadvantages of cumbersome operation, environmentally unfriendly, and high cost. Herein, one type of MXene material, annealed delaminated Ti3C2Tz (AD-Ti3C2Tz) electrodes, obtained by vacuum-assisted filtration and annealing processes, was directly used as free-standing anodes for both lithium-ion batteries and sodium-ion batteries without the use of binder or carbon additives. Electrochemical analysis showed that the non-diffusion-controlled redox reaction dominates the electrochemical behavior of the AD-Ti3C2Tz electrode. Furthermore, the AD-Ti3C2Tz electrode exhibits good electrochemical performance without adding conductive carbon in lithium-ion and sodium-ion batteries. For example, the lithium storage capacity was 89 mAh g−1 after 2000 cycles at a specific current of 1 A g−1. The sodium storage capacity is 108 mAh g−1 and 71 mAh g−1 at 0.02 A g−1 and 2 A g−1, respectively. After AD-Ti3C2Tz electrodes reach the end of their battery life, facile direct recycling processes were employed to recover the electrodes and the capacity recovery rate is above 90 %. Besides, the cycled MXene electrodes can be easily oxidized into TiO2/C hybrids with adjustable carbon content by changing the heat-treatment temperature in CO2 flow. The obtained TiO2/C could be widely applied in batteries and the electrocatalysis field, which realizes the second life of cycled MXene.

Carbon nanoparticle coatings on laser-patterned stainless-steel surfaces present a solid lubrication system where the pattern’s recessions act as lubricant-retaining reservoirs. This study investigates the influence of the structural depth of line patterns coated with multi-walled carbon nanotubes (CNTs) and carbon onions (COs) on their respective potential to reduce friction and wear. Direct laser interference patterning (DLIP) with a pulse duration of 12 ps is used to create line patterns with three different structural depths at a periodicity of 3.5 µm on AISI 304 steel platelets. Subsequently, electrophoretic deposition (EPD) is applied to form homogeneous carbon nanoparticle coatings on the patterned platelets. Tribological ball-on-disc experiments are conducted on the as-described surfaces with an alumina counter body at a load of 100 mN. The results show that the shallower the coated structure, the lower its coefficient of friction (COF), regardless of the particle type. Thereby, with a minimum of just below 0.20, CNTs reach lower COF values than COs over most of the testing period. The resulting wear tracks are characterized by scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. During friction testing, the CNTs remain in contact, and the immediate proximity, whereas the CO coating is largely removed. Regardless of structural depth, no oxidation occurs on CNT-coated surfaces, whereas minor oxidation is detected on CO-coated wear tracks.

When lubrication of rolling bearings with oil or grease is not possible, for example because the lubricant evaporates in vacuum, solid lubrication by multiwall carbon nanotubes (MWCNT) is a viable alternative. To understand the mechanisms underlying MWCNT lubrication of highly loaded contacts, we combine an experimental approach with large-scale molecular dynamics (MD) simulations. Tribometry is performed on ground iron plates coated with two different types of MWCNTs by electrophoretic deposition. Although structural differences in the MWCNT materials result in slightly different running-in behavior, most of the tests converge to a steady-state coefficient of friction of 0.18. The resulting wear tracks and tribolayers are subjected to structural and chemical characterization and suggest a tribo-induced phase transformation resulting in tribolayers that consist of MWCNT fragments, iron oxide, and iron carbide nanoparticles embedded in an amorphous carbon matrix. Covalent bonding of the tribolayer to the iron surface and low carbon transfer to the alumina counter body indicate sliding at the tribolayer/ball interface as the dominant mechanism underlying MWCNT solid lubrication. MD simulations of nascent a-C tribofilms lubricated by MWCNT bundles and stacks of crossed MWCNTs reveal two different sliding regimes: a low-load regime that leaves the MWCNTs intact and a high-load regime with partial collapse of the tube structure and formation of a-C regions. The critical load for this transition increases with the filling ratio of the MWCNT and the packing density of the stacks. The former determines the stability of the MWCNT, while the latter controls the local stresses at the MWCNT crossings. For both MWCNT materials, the high-load regime is predicted for the experimental loads. This is confirmed by a remarkable agreement between transmission electron microscopy (TEM) and atomistic simulation images. Based on the findings of this work, a multistep lubrication mechanism is formulated for MWCNT coatings rubbing against alumina on an iron substrate.

Stable and efficient SnO2 electrodes are very promising for effectively degrading refractory organic pollutants in wastewater treatment. In this regard, we firstly prepared Ti3+ self-doped urchin-like rutile TiO2 nanoclusters (TiO2-xNCs) on a Ti mesh substrate by hydrothermal and electroreduction to serve as an interlayer for the deposition of Sb−SnO2. The TiO2-xNCs/Sb−SnO2 anode exhibited a high oxygen evolution potential (2.63 V vs. SCE) and strong ⋅OH generation ability for the enhanced amount of absorbed oxygen species. Thus, the degradation results demonstrated its good rhodamine B (RhB), methylene blue (MB), alizarin yellow R (AYR), and methyl orange (MO) removal performance, with the rate constant increased 5.0, 1.9, 1.9, and 4.7 times, respectively, compared to the control Sb−SnO2 electrode. RhB and AYR degradation mechanisms are also proposed based on the results of high-performance liquid chromatography coupled with mass spectrometry and quenching experiments. More importantly, this unique rutile interlayer prolonged the anode lifetime sixfold, given its good lattice match with SnO2 and the three-dimensional concave–convex structure. Consequently, this work paves a new way for designing the crystal form and structure of the interlayers to obtain efficient and stable SnO2 electrodes for addressing dye wastewater problems.

Optimizing the synergy between nanoporous carbons and ionic liquids can significantly enhance the energy density of supercapacitors. The highest energy density has been obtained as the size of porous carbon matches the size of ionic liquids, while it may result in slower charging dynamics and thus reduce the power density. Enhancing energy storage without retarding charging dynamics remains challenging. Herein, we designed porous electrodes by introducing an optimized horn-like entrance to the nanopore, which can concurrently improve supercapacitors’ charging dynamics and energy storage. Our results revealed the mechanism of improved charging lies in the gradual desolvation process and optimized ion motion paths: the former expedites the adsorption of the counterion by reducing the transitional energy barrier for ions entering the pores, and the latter accelerates the co-ion desorption and eliminates ion overfilling. Meanwhile, the enhancement of energy density could be attributed to the multi-ion coordinated migration.