Nitrogen-Doped Graphene-Like Carbon Intercalated MXene Heterostructure Electrodes for Enhanced Sodium- and Lithium-Ion Storage.

MXene is investigated as an electrode material for different energy storage systems due to layered structures and metal-like electrical conductivity. Experimental results show MXenes possess excellent cycling performance as anode materials, especially at large current densities. However, the reversible capacity is relatively low, which is a significant barrier to meeting the demands of industrial applications. This work synthesizes N-doped graphene-like carbon (NGC) intercalated Ti3C2Tx (NGC-Ti3C2Tx) van der Waals heterostructure by an in situ method. The as-prepared NGC-Ti3C2Tx van der Waals heterostructure is employed as sodium-ion and lithium-ion battery electrodes. For sodium-ion batteries, a reversible specific capacity of 305 mAh g-1 is achieved at a specific current of 20 mA g-1, 2.3 times higher than that of Ti3C2Tx. For lithium-ion batteries, a reversible capacity of 400 mAh g-1 at a specific current of 20 mA g-1 is 1.5 times higher than that of Ti3C2Tx. Both sodium-ion and lithium-ion batteries made from NGC-Ti3C2Tx shows high cycling stability. The theoretical calculations also verify the remarkable improvement in battery capacity within the NGC-Ti3C2O2 system, attributed to the additional adsorption of working ions at the edge states of NGC. This work offers an innovative way to synthesize a new van der Waals heterostructure and provides a new route to improve the electrochemical performance significantly.

Probing the Electronic Structure of Prussian Blue and Analog Films by Photoemission and Electron Energy Loss Spectroscopies.

X-ray photoelectron spectroscopy (XPS) and reflection electron energy loss spectroscopy (REELS) were employed to characterize the electronic properties of Prussian blue (PB) and its analogs when electrodeposited over metal-decorated carbon nanotubes (CNTs). Through an investigation of the influence of carbon nanotubes (CNTs) and preparation conditions on the electronic structure, valuable insights were obtained regarding their effects on electrochemical properties. XPS analysis enabled the probing of the chemical composition and oxidation states of the film materials, unveiling synthesis-driven variations in their electronic properties. REELS provided information on energy loss and electronic transitions, enabling further characterization of the changes in the electronic structure induced by different preparation methods. Such findings emphasize the importance of surface characterization to understand how the unique electronic properties of such materials can be harnessed to enhance their performance and functionality.

Mixed Cu-Fe Sulfides Derived from Polydopamine-Coated Prussian Blue Analogue as a Lithium-Ion Battery Electrode.

Batteries employing transition-metal sulfides enable high-charge storage capacities, but polysulfide shuttling and volume expansion cause structural disintegration and early capacity fading. The design of heterostructures combining metal sulfides and carbon with an optimized morphology can effectively address these issues. Our work introduces dopamine-coated copper Prussian blue (CuPB) analogue as a template to prepare nanostructured mixed copper-iron sulfide electrodes. The material was prepared by coprecipitation of CuPB with in situ dopamine polymerization, followed by thermal sulfidation. Dopamine controls the particle size and favors K-rich CuPB due to its polymerization mechanism. While the presence of the coating prevents particle agglomeration during thermal sulfidation, its thickness demonstrates a key effect on the electrochemical performance of the derived sulfides. After a two-step activation process during cycling, the C-coated KCuFeS2 electrodes showed capacities up to 800 mAh/g at 10 mA/g with nearly 100% capacity recovery after rate handling and a capacity of 380 mAh/g at 250 mA/g after 500 cycles.

Porous Mixed-Metal Oxide Li-Ion Battery Electrodes by Shear-Induced Co-assembly of Precursors and Tailored Polymer Particles.

Due to their various applications, metal oxides are of high interest for fundamental research and commercial usage. Per applications as catalysts or electrochemical devices, the tailored design of metal oxides featuring a high specific surface area and additional functionalities is of the utmost importance for the performance of the resulting materials. We report a new method for preparing free-standing films consisting of hierarchically porous metal oxides (titanium and niobium based) by combining emulsion polymerization and shear-induced monodisperse particle self-assembly in the presence of sol-gel precursors. After thermal treatment, the resulting porous materials can be used as electrodes in Li-ion batteries. The titanium and niobium sol-gel precursors were partially immobilized to the surface of organic core-interlayer particles featuring hydroxyl groups to obtain hybrid organic-inorganic particles through the melt-shear organization process. Free-standing particle-based films, in analogy to elastomeric opal films and colloidal crystals, can be prepared in a convenient one-step preparation process. After thermal treatment, ordered pores are obtained, while the pristine metal oxide precursor shell can be converted to the (mixed) metal oxide matrix. Heat treatment under CO2 leads to mixed-TiNb oxide/carbon hybrid materials. The highly porous derivative structure enhances electrolyte permeation. When tested as Li-ion battery electrodes, it shows a specific capacity of 335 mAh·g-1 at a rate of 10 mA·g-1. After 1000 cycles at 250 mA·g-1, the electrodes still provided a specific capacity of 191 mAh·g-1.

Structural and chemical characterization of MoO2/MoS2 triple-hybrid materials using electron microscopy in up to three dimensions.

This work presents the synthesis of MoO2/MoS2 core/shell nanoparticles within a carbon nanotube network and their detailed electron microscopy investigation in up to three dimensions. The triple-hybrid core/shell material was prepared by atomic layer deposition of molybdenum oxide onto carbon nanotube networks, followed by annealing in a sulfur-containing gas atmosphere. High-resolution transmission electron microscopy together with electron diffraction, supported by chemical analysis via energy dispersive X-ray and electron energy loss spectroscopy, gave proof of a MoO2 core covered by few layers of a MoS2 shell within an entangled network of carbon nanotubes. To gain further insights into this complex material, the analysis was completed with 3D electron tomography. By using Z-contrast imaging, distinct reconstruction of core and shell material was possible, enabling the analysis of the 3D structure of the material. These investigations showed imperfections in the nanoparticles which can impact material performance, i.e. for faradaic charge storage or electrocatalysis.

Ionic liquid-based synthesis of MXene.

MAX phases are etched using an ionic liquid-water mixture to produce titanium carbide MXenes. The process avoids the use of any acid. Hydrolysis of the fluorine-containing ionic liquid leads to the selective removal of Al, while the ionic liquid is intercalated in-between the transition metal carbide layers.

Low voltage operation of a silver/silver chloride battery with high desalination capacity in seawater.

Technologies for the effective and energy efficient removal of salt from saline media for advanced water remediation are in high demand. Capacitive deionization using carbon electrodes is limited to highly diluted salt water. Our work demonstrates the high desalination performance of the silver/silver chloride conversion reaction by a chloride ion rocking-chair desalination mechanism. Silver nanoparticles are used as positive electrodes while their chlorination into AgCl particles produces the negative electrode in such a combination that enables a very low cell voltage of only Δ200 mV. We used a chloride-ion desalination cell with two flow channels separated by a polymeric cation exchange membrane. The optimized electrode paring between Ag and AgCl achieves a low energy consumption of 2.5 kT per ion when performing treatment with highly saline feed (600 mM NaCl). The cell affords a stable desalination capacity of 115 mg g-1 at a charge efficiency of 98%. This performance aligns with a charge capacity of 110 mA h g-1.

Photoanode for Aqueous Dye-Sensitized Solar Cells based on a Novel Multicomponent Thin Film.

Most of the dye-sensitized solar cells (DSSCs) developed so far use organic electrolytes and water-sensible sensitizers. The search for aqueous DSSCs, a promising technology for solar-energy conversion, implies finding materials that are stable in aqueous solution. In this study, Prussian blue (PB) was utilized as an innovative sensitizer in a photoanode for DSSCs and a novel synthetic approach to a carbon nanotubes/TiO2 /PB nanocomposite thin film was developed. The photoresponse was evaluated in a total aqueous electrolyte, and photocurrents of 600 µA cm-2 were achieved.

Design of a Prussian Blue Analogue/Carbon Nanotube Thin-Film Nanocomposite: Tailored Precursor Preparation, Synthesis, Characterization, and Application.

Multi-walled carbon nanotubes (MWCNTs) filled with different species of cobalt (metallic cobalt, cobalt oxide) were synthesized by a chemical vapor deposition method through cobaltocene pyrolysis. A systematic study was performed to correlate different experimental conditions with the structure and characteristics of the obtained material. Thin films of Co-filled CNTs were deposited over conductive substrates through a liquid-liquid interfacial method and were used for cobalt hexacyanoferrate (CoHCFe) electrodeposition by an innovative route in which the Co species encapsulated in the CNTs were employed as reactants. The CNT/CoHCFe films were characterized by different spectroscopic, microscopic, and electrochemical techniques and presented high electrochemical stability in different media. The nanocomposites were applied as both an electrochemical sensor to H2 O2 and a cathode for ion batteries and showed limits of detection at approximately 3.7 nmol L(-1) and a capacity of 130 mAh g(-1) at a current density of 5 A g(-1) .

Multifunctional carbon nanotubes/ruthenium purple thin films: preparation, characterization and study of application as sensors and electrochromic materials.

This work reports the preparation, characterization and application as both electrochromic materials and electrochemical sensors of novel materials: carbon nanotubes/ruthenium purple nanocomposites. Using an innovative route based on a heterogeneous electrochemical reaction involving iron oxide species encapsulated within the cavities of the carbon nanotubes, the nanocomposite materials were obtained as transparent thin films deposited over transparent electrodes. Several experimental parameters related to the nanocomposite synthesis were evaluated and related to the characteristics of the obtained materials, such as morphology and stability. The films were characterized by UV-Vis and Raman spectroscopy, scanning electron microscopy, X-ray diffraction, cyclic voltammetry and UV-Vis and Raman spectroelectrochemistry. Four different materials were applied as H2O2 sensors and exhibited impressive analytical parameters, including a limit of detection of 1.27 nmol L(-1) and a sensitivity of 39.6 A M(-1) cm(-2). These nanocomposites also showed great electrochromic properties, with high stability and coloration efficiency over 95% maintained during stability cycles.