Operando Gravimetric and Energy Loss Analysis of NaV(PO)F Composite Films by Electrochemical Quartz Microbalance with Dissipation Monitoring.

The rising demand for energy storage calls for technological advancements to address the growing needs. In this context, sodium-ion (Na-ion) batteries have emerged as a potential complementary technology to lithium-ion batteries (Li-ion). Among other materials, NaV(PO)F (NVPF) is a promising cathode for Na-ion batteries due to its high operating voltage and good energy density.

Advanced characterization of confined electrochemical interfaces in electrochemical capacitors.

The advancement of high-performance fast-charging materials has significantly propelled progress in electrochemical capacitors (ECs). Electrochemical capacitors store charges at the nanoscale electrode material-electrolyte interface, where the charge storage and transport mechanisms are mediated by factors such as nanoconfinement, local electrode structure, surface properties and non-electrostatic ion-electrode interactions. This Review offers a comprehensive exploration of probing the confined electrochemical interface using advanced characterization techniques.

Hard carbon from a sugar derivative for next-generation sodium-ion batteries.

Sodium-ion batteries have emerged as a promising secondary battery system due to the abundance of sodium resources. One of the boosters for accelerating the practical application of sodium-ion batteries is the innovation in anode materials. This study focuses on developing a high-performance hard carbon anode material derived from hydroxymethylfurfural, produced from carbohydrates, using a straightforward thermal condensation method.

Revealing Ion Adsorption and Charging Mechanisms in Layered Metal-Organic Framework Supercapacitors with Solid-State Nuclear Magnetic Resonance.

Conductive layered metal-organic frameworks (MOFs) have demonstrated promising electrochemical performances as supercapacitor electrode materials. The well-defined chemical structures of these crystalline porous electrodes facilitate structure-performance studies; however, there is a fundamental lack in the molecular-level understanding of charge storage mechanisms in conductive layered MOFs. To address this, we employ solid-state nuclear magnetic resonance (NMR) spectroscopy to study ion adsorption in nickel 2,3,6,7,10,11-hexaiminotriphenylene, Ni(HITP).

Nanoscale Surface and Bulk Electronic Properties of TiCT MXene Unraveled by Multimodal X-Ray Spectromicroscopy.

2D layered materials, such as transition metal carbides or nitrides, known as MXenes, offer an ideal platform to investigate charge transfer processes in confined environment, relevant for energy conversion and storage applications. Their rich surface chemistry plays an essential role in the pseudocapacitive behavior of MXenes. However, the local distribution of surface functional groups over single flakes and within few- or multilayered flakes remains unclear.

Understanding Electrolyte Ion Size Effects on the Performance of Conducting Metal-Organic Framework Supercapacitors.

Layered metal-organic frameworks (MOFs) have emerged as promising materials for next-generation supercapacitors. Understanding how and why electrolyte ion size impacts electrochemical performance is crucial for developing improved MOF-based devices. To address this, we investigate the energy storage performance of Cu(HHTP) (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with a series of 1 M tetraalkylammonium tetrafluoroborate (TAABF) electrolytes with different cation sizes.

Cation desolvation-induced capacitance enhancement in reduced graphene oxide (rGO).

Understanding the local electrochemical processes is of key importance for efficient energy storage applications, including electrochemical double layer capacitors. In this work, we studied the charge storage mechanism of a model material - reduced graphene oxide (rGO) - in aqueous electrolyte using the combination of cavity micro-electrode, operando electrochemical quartz crystal microbalance (EQCM) and operando electrochemical dilatometry (ECD) tools. We evidence two regions with different charge storage mechanisms, depending on the cation-carbon interaction.

Role of Surface Terminations for Charge Storage of TiCT MXene Electrodes in Aqueous Acidic Electrolyte.

In this study, we used 2-Dimmensionnal TiC MXene as model materials to understand how the surface groups affect their electrochemical performance. By adjusting the nature of the surface terminations (Cl-, N/O-, and O-) of TiC MXene through a molten salt approach, we could change the spacing between MXene layers and the level of water confinement, resulting in significant modifications of the electrochemical performance in acidic electrolyte. Using a combination of techniques including in-operando X-ray diffraction and electrochemical quartz crystal microbalance (EQCM) techniques, we found that the presence of confined water results in a drastic transition from an almost electrochemically inactive behavior for Cl-terminated TiC to an ideally fast pseudocapacitive signature for N,O-terminated TiC MXene.

Carbon Materials Prepared from Invading Pelagic Sargassum for Supercapacitors' Electrodes.

Since 2011, substantial amounts of pelagic Sargassum algae have washed up along the Caribbean beaches and the Gulf of Mexico, leading to negative impacts on the economy and the environment of those areas. Hence, it is now crucial to develop strategies to mitigate this problem while valorizing such invasive biomass. This work deals with the successful exploitation of this pelagic Sargassum seaweed for the fabrication of carbon materials that can be used as electrodes for supercapacitors.

Composite Mn-Co electrode materials for supercapacitors: why the precursor's morphology matters!

In the energy storage field, an electrode material must possess both good ionic and electronic conductivities to perform well, especially when high power is needed. In this context, the development of composite electrode materials combining an electrochemically active and good ionic conductor phase with an electronic conductor appears as a perfectly adapted approach to generate a synergetic effect and optimize the energy storage performance. In this work, three layered MnO phases with various morphologies (veils, nanoplatelets and microplatelets) were combined with electronic conductor cobalt oxyhydroxides with different platelet sizes (∼20 nm 70 nm wide), to synthesize 6 different composites by exfoliation and restacking processes.

Synthesis of MAX Phase Nanofibers and Nanoflakes and the Resulting MXenes.

Layered ternary carbides and nitrides, also known as MAX phases, have attracted enormous attention for many applications, especially as precursors to produce 2D metal carbides and nitrides called MXenes. However, it is still challenging to tune and control the shape/morphology of MAX phase particles at the nanoscale, as they are typically manufactured as large grains using ceramic technology. Herein, nanostructured Ti-Al-C MAX phases with fine-tuned morphology of nanofibers and nanoflakes are prepared by using 1D and 2D carbon precursors at a synthesis temperature of 900 °C.

Unraveling the Capacitive Charge Storage Mechanism of Nitrogen-Doped Porous Carbons by EQCM and ssNMR.

Fundamental understanding of ion electroadsorption processes in porous electrodes on a molecular level provides important guidelines for next-generation energy storage devices like electric double layer capacitors (EDLCs). Porous carbons functionalized by heteroatoms show enhanced capacitive performance, but the underlying mechanism is still elusive, due to the lack of reliable tools to precisely identify multiple N species and establish clear structure property relations. Here, we use advanced analytical techniques such as low-temperature solid-state NMR (ssNMR) and electrochemical quartz crystal microbalance (EQCM) to relate the complex nitrogen functionalities to the charging mechanisms and capacitive performance.

Mitigation of Edge and Surface States Effects in Two-Dimensional WS for Photocatalytic H Generation.

Large scale development of the 2D transition metal di-chalcogenides (TMDC) relies on landmark improvement in performance, which could emerge from nanostructuration. Using p-WS nanoflakes with different degrees of exfoliation and fracturing, perspectives were provided to develop high-surface-area 2D p-WS films for the photocatalytic hydrogen generation. The critical role of inter-nanoflakes contacts within high-surface-area 2D films was demonstrated, highlighting the benefit of plane/plane versus edge/plane contacts.

Exfoliation and Delamination of TiCT MXene Prepared Molten Salt Etching Route.

MXenes are two-dimensional metal carbides or nitrides that are currently proposed in many applications thanks to their unique attributes including high conductivity and accessible surface. Recently, a synthetic route was proposed to prepare MXenes from the molten salt etching of precursors allowing for the preparation of MXene (denoted as MS-MXenes, for molten salt MXene) with tuned surface termination groups, resulting in improved electrochemical properties. However, further delamination of as-prepared multilayer MS-MXenes still remains a major challenge.

Li-ion storage properties of two-dimensional titanium-carbide synthesized via fast one-pot method in air atmosphere.

Structural bidimensional transition-metal carbides and/or nitrides (MXenes) have drawn the attention of the material science research community thanks to their unique physical-chemical properties. However, a facile and cost-effective synthesis of MXenes has not yet been reported. Here, using elemental precursors, we report a method for MXene synthesis via titanium aluminium carbide formation and subsequent in situ etching in one molten salt pot.

Electrochemical Characterization of Single Layer Graphene/Electrolyte Interface: Effect of Solvent on the Interfacial Capacitance.

The development of the basic understanding of the charge storage mechanisms in electrodes for energy storage applications needs deep characterization of the electrode/electrolyte interface. In this work, we studied the charge of the double layer capacitance at single layer graphene (SLG) electrode used as a model material, in neat (EMIm-TFSI) and solvated (with acetonitrile) ionic liquid electrodes. The combination of electrochemical impedance spectroscopy and gravimetric electrochemical quartz crystal microbalance (EQCM) measurements evidence that the presence of solvent drastically increases the charge carrier density at the SLG/ionic liquid interface.

Nanoporous carbon for electrochemical capacitive energy storage.

The urgent need for efficient energy storage devices has stimulated a great deal of research on electrochemical double layer capacitors (EDLCs). This review aims at summarizing the recent progress in nanoporous carbons, as the most commonly used EDLC electrode materials in the field of capacitive energy storage, from the viewpoint of materials science and characterization techniques. We discuss the key advances in the fundamental understanding of the charge storage mechanism in nanoporous carbon-based electrodes, including the double layer formation in confined nanopores.

A general Lewis acidic etching route for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte.

Two-dimensional carbides and nitrides of transition metals, known as MXenes, are a fast-growing family of materials that have attracted attention as energy storage materials. MXenes are mainly prepared from Al-containing MAX phases (where A = Al) by Al dissolution in F-containing solution; most other MAX phases have not been explored. Here a redox-controlled A-site etching of MAX phases in Lewis acidic melts is proposed and validated by the synthesis of various MXenes from unconventional MAX-phase precursors with A elements Si, Zn and Ga.

Ultrafast Synthesis of Calcium Vanadate for Superior Aqueous Calcium-Ion Battery.

Recently, multivalent aqueous calcium-ion batteries (CIBs) have attracted considerable attention as a possible alternative to Li-ion batteries. However, traditional Ca-ion storage materials show either limited rate capabilities and poor cycle life or insufficient specific capacity. Here, we tackle these limitations by exploring materials having a large interlayer distance to achieve decent specific capacities and one-dimensional architecture with adequate Ca-ion passages that enable rapid reversible (de)intercalation processes.

Charge Storage Mechanisms of Single-Layer Graphene in Ionic Liquid.

Graphene-based carbon materials are promising candidates for electrical double-layer (EDL) capacitors, and there is considerable interest in understanding the structure and properties of the graphene/electrolyte interface. Here, electrochemical impedance spectroscopy (EIS) and electrochemical quartz crystal microbalance (EQCM) are used to characterize the ion fluxes and adsorption on single-layer graphene in neat ionic liquid (EMI-TFSI) electrolyte. It is found that a positively charged ion-species desorption and ion reorganization dominate the double-layer charging during positive and negative polarizations, respectively, leading to the increase in EDL capacitance with applied potential.

Fast Electrochemical Storage Process in Sputtered NbO Porous Thin Films.

The formation of a thin film electrode exhibiting high capacity and high rate capabilities is challenging in the field of miniaturized electrochemical energy storage. Here, we present an elegant strategy to tune the morphology and the properties of sputtered porous NbO thin films deposited on Si-based substrates via the magnetron sputtering deposition technique. Kinetic analysis of the redox reactions is studied to qualify the charge storage process, where we observe a non-diffusion-controlled mechanism within the porous niobium pentoxide thin film.

Sparsely Pillared Graphene Materials for High-Performance Supercapacitors: Improving Ion Transport and Storage Capacity.

Graphene-based materials are extensively studied as promising candidates for supercapacitors (SCs) owing to the high surface area, electrical conductivity, and mechanical flexibility of graphene. Reduced graphene oxide (RGO), a close graphene-like material studied for SCs, offers limited specific capacitances (100 F·g) as the reduced graphene sheets partially restack through π-π interactions. This paper presents pillared graphene materials designed to minimize such graphitic restacking by cross-linking the graphene sheets with a bifunctional pillar molecule.

Tracking Ionic Rearrangements and Interpreting Dynamic Volumetric Changes in Two-Dimensional Metal Carbide Supercapacitors: A Molecular Dynamics Simulation Study.

We present a molecular dynamics simulation study achieved on two-dimensional (2D) Ti C T MXenes in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] [TFSI] ) electrolyte. Our simulations reproduce the different patterns of volumetric change observed experimentally for both the negative and positive electrodes. The analysis of ionic fluxes and structure rearrangements in the 2D material provide an atomic scale insight into the charge and discharge processes in the layer pore and confirm the existence of two different charge-storage mechanisms at the negative and positive electrodes.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species.