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The current work delivers preparation of MXene-based magnetic nanohybrid coating for flexible electronic applications. Herein, we report carbon dot-triggered photopolymerized polynorepinepherene (PNE)-coated MXene and iron oxide hybrid deposited on the cellulose microporous membrane via a vacuum-assisted filtration strategy. The surface morphologies have been monitored by scanning electron microscopy analysis, and the coating thickness was evaluated by the gallium-ion-based focused ion beam method. Coated membranes have been tested against uniaxial tensile stretching and assessed by their fracture edges in order to assure flexibility and mechanical strength. Strain sensors and electromagnetic interference (EMI) shielding have both been tested on the material because of its electrical conductivity. The bending strain sensitivity has been stringent because of their fast 'rupture and reform' percolation network formation on the coated surface. Increased mechanical strength, solvent tolerance, cyclic deformation tolerance, and EMI shielding performance were achieved by decreasing interstitial membrane porosity. Considering a possible application, the membrane also has been tested against simulated static and dynamic water flow conditions that could infer its excellent robustness which also has been confirmed by elemental analysis via ICP-MS. Thus, as of nurturing the works of the literature, it could be believed that the developed material will be an ideal alternative of flexible lightweight cellulose for versatile electronic applications.

Li and Mn-rich nickel cobalt manganese oxide (LMR-NCM) is one of the most promising cathode materials for realizing next-generation Li-ion batteries due to its high specific capacity of >250 mA h g-1 and operating potential > 4.5 V. Nevertheless, being plagued by severe capacity fading and voltage decay, the commercialization of LMR-NCM appears to be a distant goal. The anionic activity of oxygen and associated phase transformations are the reasons behind the unstable electrochemical performance. The tendency of LMR-NCM to react with CO2 and moisture further makes it prone to interfacial instability and degradation. Here, we report a neoteric method to mitigate the stability issues and improve the electrochemical performance of LMR-NCM by changing the electronic configuration of constituting O and transition metals via diethylzinc-assisted atomic surface reduction (Zn-ASR) using an extremely facile protocol. With the proposed Zn-ASR, a 2-3 nm thin layer of a reduced surface enriched with complex ZnOx or ZnOxRy was obtained on the LMR-NCM particles. X-ray photoelectron spectroscopy suggested the transfer of ethyl groups of diethylzinc to O atoms on the LMR-NCM surface, which ultimately led to the reduction of near-surface Mn and Ni atoms and impeded irreversible anionic activity. The presence of ZnOx/ZnOxRy also resulted in superior charge transfer and resistance against HF. As a result, in contrast to LMR-NCM, the Zn-ASR-treated sample exhibited substantially improved rate capabilities, facilitated charge transfer, enhanced capacity retention, reduced parasitic reactions, and long-term stability as reflected from in-depth electrochemical analysis, in operando gaseous evolution studies, and post-mortem microscopic analysis.

The current work presents a facile and green synthesis of carbon quantum dots (C-dots), which could serve as initiators for polymerization. Herein, C-dots have been synthesized from an easily available green herb, dill leaves, by a single-step hydrothermal method. These C-dots were efficiently utilized as initiators for the photopolymerization of the polymer poly(norepinephrine) (PNE) for the first time. The photopolymerization is discussed by a factorial design, and the optimized synthesis conditions were evaluated by a third-order regression model of three reaction parameters: monomer concentration, C-dots concentration, and UV exposure time. The sign convention of the factorial design mode indicated that monomer concentration and time of exposure are the most important factors for polymerization. The photopolymerized poly(norepinephrine) was extensively studied using Fourier transform infrared (FTIR) analysis, X-ray photoelectron spectroscopy (XPS), mass spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurement, and thermogravimetric analysis (TGA). UV-assisted deposition of PNE on six different types of substrates was performed, and their water contact angle and surface morphology were studied to evaluate the coating. This UV-triggered polymerization technique was further applied to fabricate sandwich-like composite catalyst MXene/poly(norepinephrine)/copper nanoparticles. This catalyst displayed good performance in the reduction of 4-NP (4-nitrophenol) at ambient temperature, and the first-order rate constant of the catalysis was 9.39 × 10-3 s-1. The reusability of the catalyst was evaluated in terms of the conversion factor. After 10 catalytic cycles, the conversion to catalyze 4-NP was still greater than 91%. The catalytic performance was also evaluated in the continuous flow condition through a membrane, fabricated from a cellulose filter paper coated with MXene/poly(norepinephrine)/copper nanoparticles. This composite catalyst not only offers a practical mode for the catalytic reaction of MXene-based materials but also lays down the foundation for the development of new catalysts.

In a lithium–sulfur battery (LSB) discharge process, elemental sulfur is reduced to Li2S via a multi-step process. The soluble lithium-polysulfide (PS) (Li2Sn) intermediate species then diffuses th...

Degradation processes at the cathode–electrolyte interface are a major limitation in the development of high-energy lithium-ion rechargeable batteries. Deposition of protective thin coating layers on the surface of high-energy cathodes is a promising approach to control interfacial reactions. However, rational design of effective protection layers is limited by the scarcity of analytical tools that can probe thin, disordered, and heterogeneous phases. Here we propose a new structural approach based on solid-state nuclear magnetic resonance spectroscopy coupled with dynamic nuclear polarization (DNP) for characterizing thin coating layers. We demonstrate the approach on an efficient alkylated LixSiyOz coating layer. By utilizing different sources for DNP, exogenous from nitroxide biradicals and endogenous from paramagnetic metal ion dopants, we reveal the outer and inner surface layers of the deposited artificial interphase and construct a structural model for the coating. In addition, lithium isotope exchange experiments provide direct evidence for the function of the surface layer, shedding light on its role in the enhanced rate performance of coated cathodes. The presented methodology and results advance us in identifying the key properties of effective coatings and may enable rational design of protective and ion-conducting surface layers.

The commercialization of the high energy, lithium, and manganese-rich NCM (LMR-NCM) is impeded by its complex interfacial electrochemical processes, oxygen release, and surface degradation. Here, we introduced t-butyl-dimethylsilyllithium as a single-source precursor for depositing LixSiyOz with an integrated network of siloxane moieties as an artificial cathode/electrolyte interphase (ACEI) which stabilizes LMR-NCM by mitigating oxygen release, electrolyte degradation and preventing fractures. Using solid-state NMR coupled with dynamic nuclear polarization, detailed molecular-level characterization of the ACEI is presented. The proposed CEI enabled improved energy-density at high rates (644 Wh.kg-1, compared to uncoated material with 457 Wh.kg-1 at 4C) with suppressed parasitic reactions and O2 evolution. The efficacy of the CEI is demonstrated in full graphite/LMR-NCM pouch cells with ~ 35% enhanced capacity and >80% capacity retention over 200 cycles. Altogether, these results present the importance of careful selection and design of surface chemistry for stabilizing the electrode/electrolyte interphase in challenging battery chemistries.

Exploring and identifying efficient materials with operative active sites for electrochemical oxygen evolution reaction (OER) is of paramount importance for the future of energy conversion technolo...

We demonstrate a novel surface modification of Li- and Mn-rich cathode materials 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 for lithium-ion batteries (high-energy Ni-Co-Mn oxides, HE-NCM) via their heat treatment with trimesic acid (TA) or terephthalic acid at 600 °C under argon. We established the optimal regimes of the treatment-the amounts of HE-NCM, acid, temperature, and time-resulting in a significant improvement of the electrochemical behavior of cathodes in Li cells. It was shown that upon treatment, some lithium is leached out from the surface, leading to the formation of a surface layer comprising rock-salt-like phase Li0.4Ni1.6O2. The analysis of the structural and surface studies by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy confirmed the formation of the above surface layer. We discuss the possible reactions of HE-NCM with the acids and the mechanism of the formation of the new phases, Li0.4Ni1.6O2 and spinel. The electrochemical characterizations were performed by testing the materials versus Li anodes at 30 °C. Importantly, the electrochemical results disclose significantly improved cycling stability (much lower capacity fading) and high-rate performance for the treated materials compared to the untreated ones. We established a lower evolution of the voltage hysteresis with cycling for the treated cathodes compared to that for the untreated ones. Thermal studies by differential scanning calorimetry also demonstrated lower (by ∼32%) total heat released in the reactions of the materials treated with fluoroethylene carbonate (FEC)-dimethyl carbonate (DEC)/LiPF6 electrolyte solutions, thus implying their significant surface stabilization because of the surface treatment. It was established by a postmortem analysis after 400 cycles that a lower amount of transition-metal cations dissolved (especially Ni) and a reduced number of surface cracks were formed for the 2 wt % TA-treated HE-NCMs compared to the untreated ones. We consider the proposed method of surface modification as a simple, cheap, and scalable approach to achieve a steady and superior electrochemical performance of HE-NCM cathodes.

Na3V2(PO4)2F3 (NVPF) has been extensively studied, and has demonstrated excellent electrochemical activity in Na-ion batteries owing to its high reversible specific capacity and stability. The direct chemical synthesis of a Li analogue of NVPF (LVPF) is aided by the high thermodynamic stability of intermediate products. Even more challenging is the synthesis of LVPF with a well-controlled uniform morphology and a stable crystal structure. Herein, an electrochemical ion exchange approach was used to synthesize Na0.7Li2.3V2(PO4)F3 (N0.7L2.3VPF), an isostructural composition of Li3V2(PO4)F3. This compound was prepared via lithiation of Na0.7V2(PO4)F3 with a hierarchical morphology prepared by desodiation of NVPF. We track the phase formation, reversible structural transformation from Pnnm to Cmc21 and back to Pnnm. An initial specific discharge capacity of 185 mA h g−1 and two distinct voltage plateaus visualize the prominence of N0.7L2.3VPF as a cathode material for LIBs. It exhibits a specific discharge capacity of 173, 159, 154, 134 and 114 mA h g−1 at 45, 105, 135, 265, and 535 mA g−1 respectively along with >98% coulombic efficiency, which indicates pronounced electrochemical activity at high current rates due to better diffusivity of smaller Li+ ions than Na+ ions through the partially occupied alkali metal sites in the lattice. Long-term cycling at 45 mA g−1 exhibits 173 mA h g−1 with 96% of capacity retention for 200 cycles. This stable performance further indicates the prominence of N0.7L2.3VPF HMS as a cathode for LIBs. Our findings provide a strategic pathway towards controlling the morphology and crystal structure and shed light on its importance in realization as a cathode material for LIBs.

Catalyst poisoning is a prominent issue, reducing the lifetime of catalysts and increasing the costs of the processes that rely on them. The electrocatalysts that enable green energy conversion and storage, such as proton exchange membrane fuel cells and hydrogen bromine redox flow batteries, also suffer from this issue, hindering their utilization. Current solutions to protect electrocatalysts from harmful species fall short of effective selectivity without inhibiting the required reactions. This article describes the protection of a standard 50% Pt/C catalyst with a V2O5 coating through atomic layer deposition (ALD). The ALD selectively deposited V2O5 on the Pt, which enhanced hydrogen transport to the Pt surface and resulted in a higher mass activity in alkaline electrolytes. Cyclic voltammetry and X-ray photoelectron spectroscopy showed that the Pt was protected by the coating in the HBr/Br2 electrolyte which dissolved the uncoated 50% Pt/C in under 3 min.

High-Ni-rich layered oxides [e.g., LiNi

To mitigate the associated challenges of instability and capacity improvement in Na

Disordered carbons are promising anode materials for sodium ion batteries. However, a major drawback of these materials is their low coulombic efficiency in the first cycles, which indicates parasitic reactions. Such reactions can be suppressed by alumina coating on the surface of the anodic materials; more ions are then available for electrochemical activity, and less electrolyte solution is lost. On the other hand, some pores and surface edge sites are passivated by the coating and are no longer available for reversible reaction with sodium ions; hence, their contribution is eliminated, leading to reduction in specific capacity. We show herein that electrochemical insertion of sodium ions into carbon anodes prior to alumina coating has a double positive effect on anode perfomances, meaning preventing passivation and maintaining high specific capacity. We show that the artificial layer still prevented parasitic reactions, while the pores and surface edge sites retained electrochemical activity. The capacity values were thus restored and even became higher as a result of preventing the development of a surface layer. Ultraviolet photoelectron spectroscopy measurements assessed the energetic states of the electrodes and confirmed that the alumina coating forms a barrier for interfacial electron transfer from the electrode to the solution at any polarization stage.

In the present work, a simple and agile methodology for atomic surface reduction of interfaces is introduced. Using a surface directed vapor phase reaction, at relatively low temperature, we show that a highly reactive and volatile molecule can be used to selectively reduce the interface, without changing the bulk of the treated material, and without the need of alternating sequence of multiple precursors, normally involved in ALD. The model system we use to demonstrate the efficacy, and potential of our approach is trimethyl aluminum, and high energy Li and Mn rich cathode (HE-NCM) as the functional material of interest. We demonstrate that with the proposed method, the particles of HE-NMC were conformally coated with ~ 3 nm amorphous layer of the reduced surface in less than 1 h (including the cooling time),as witnessed using HR-TEM. XPS and solid-state NMR, further confirmed that surface treatment was successfully achieved using the proposed method and is well explained by DFT calculations. Utilizing online electrochemical mass spectrometry (OEMS), we show in-operando that this amorphous layer helps to suppress parasitic reactions under extreme electrochemical conditions as indicated by the significant reduction in oxygen and CO2 evolution. The surface treatment further resulted in enhancement in specific capacity during the first cycle. This methodology provides a non-conventional path to achieve thin layer surface modification under facile conditions, and opens a new way to meet the requirements of surface modification strategies for improving the performance of electrode materials without utilizing expensive instrumentation and high temperature processes.

Rechargeable metal–sulfur batteries (RMSBs) represent one of the most attractive electrochemical systems in terms of energy density and cost. In most of the proposed systems, the anode side is metallic and the cathode side is elemental sulfur impregnated in a porous matrix. Despite the relatively low voltage of these systems, they attract a lot of attention and are considered to be very promising as next-generation batteries for the following reasons: (1) utilization of active metal anodes enables a leap in specific energy due to the high capacity of metal anodes in comparison to intercalation compounds, (2) sulfur as a cathode exhibits high theoretical specific capacity (1675 mAh/g), and (3) system components make RMSBs low-cost, less toxic batteries. Nevertheless, the high reactivity of metallic anodes (e.g., Li, Na, Mg, and Al) and the solubility of sulfur species in the electrolyte render these batteries unstable and hinder their practical realization. In this Perspective, we focus on rechargeable sul...

The current work presents a facile and green synthesis of carbon quantum dots (C-dots), which could serve as initiators for polymerization. Herein, C-dots have been synthesized from an easily available green herb, dill leaves, by a single-step hydrothermal method. These C-dots were efficiently utilized as initiators for the photopolymerization of the polymer poly(norepinephrine) (PNE) for the first time. The photopolymerization is discussed by a factorial design, and the optimized synthesis conditions were evaluated by a third-order regression model of three reaction parameters: monomer concentration, C-dots concentration, and UV exposure time. The sign convention of the factorial design mode indicated that monomer concentration and time of exposure are the most important factors for polymerization. The photopolymerized poly(norepinephrine) was extensively studied using Fourier transform infrared (FTIR) analysis, X-ray photoelectron spectroscopy (XPS), mass spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurement, and thermogravimetric analysis (TGA). UV-assisted deposition of PNE on six different types of substrates was performed, and their water contact angle and surface morphology were studied to evaluate the coating. This UV-triggered polymerization technique was further applied to fabricate sandwich-like composite catalyst MXene/poly(norepinephrine)/copper nanoparticles. This catalyst displayed good performance in the reduction of 4-NP (4-nitrophenol) at ambient temperature, and the first-order rate constant of the catalysis was 9.39 × 10

Metal-support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized reactivity was mainly detected with small (1-5 nm) oxide-supported Au nanoparticles and correlated to highly reactive sites at the oxide-metal interface. However, catalytically active sites are not necessarily restricted to the interface but reside as well on the Au surface. Uncovering the interconnection between reactive sites located at the interface and those situated at the metal surface is of crucial importance for understanding the reaction mechanism on Au nanoparticles. Herein, high-spatial-resolution IR nanospectroscopy measurements were conducted to map the localized reactivity in hydrogenation reactions on oxide-supported Au particles while using nitro-functionalized ligands as probes molecules. Comparative analysis of the reactivity pattern on single particles supported on various oxides revealed that oxide-dependent reactivity enhancement was not limited to the oxide-metal interface but was detected throughout the Au particle, leading to site-independent reactivity. These results indicate that reactive Au sites on both the oxide-metal interface and metal surface can activate the nitro groups toward hydrogenation reactions. The observed influence of oxide support (TiO2 > SiO2 > Al2O3) on the overall reactivity pattern specified that hydrogen dissociation occurred at the oxide-metal interface, followed by highly efficient intraparticle hydrogen atom diffusion to the interior parts of the Au particle. In contrast to Au particles, the oxide-metal interface had only a minor impact on the reactivity of supported Pt particles in which hydrogen dissociation and nitro group reduction were effectively activated on Pt sites. Single-particle measurements provided insights into the relative reactivity pattern of oxide-supported Au particles, revealing that the less-reactive Au metal sites can activate hydrogenation reactions in the presence of hydrogen atoms that diffuse from the Au/oxide boundary.

In recent decades, rechargeable Mg batteries (RMBs) technologies have attracted much attention because the use of thin Mg foil anodes may enable development of high‐energy‐density batteries. One of the most critical challenges for RMBs is finding suitable electrolyte solutions that enable efficient and reversible Mg cells operation. Most RMB studies concentrate on the development of novel electrolyte systems, while only few studies have focused on the practical feasibility of using pure metallic Mg as the anode material. Pure Mg metal anodes have been demonstrated to be useful in studying the fundamentals of nonaqueous Mg electrochemistry. However, pure Mg metal may not be suitable for mass production of ultrathin foils (, Ultra‐thin Mg alloy: Rechargeable magnesium batteries are considered as the most promising alternative to lithium battery technologies Similar electrochemical performance of 100 μm thick pure Mg foils and 25 μm thin and ductile AZ31 Mg alloy foils as anodes in rechargeable Mg batteries is demonstrated. Comprising Chevrel‐phase (Mo6S8) cathodes, thin foils of AZ31 Mg alloy can serve as very suitable anodes in rechargeable Mg batteries.

The need for low-cost, high-safety batteries for large-scale energy storage applications has sparked a surge in research of rechargeable aqueous batteries. While most research efforts are focused on the development of electrolyte formulations and electrode materials, it appears that the current collector impact on the battery performance is frequently overlooked. Even though the current collector is traditionally thought of as an inactive battery component, it is included in the battery energy density calculations, making its activation desirable. Furthermore, poor current collector selection can cause irreversible side reactions, resulting in rapid cell efficiency decay. Herein we propose a new approach to design current collectors that makes use of anodized Ti. The redox-active anodized Ti significantly improves the overall anode capacity and provides effective inhibition of hydrogen formation on the electrified interface. The use of TiO2 particles on an anodized Ti current collector in an aqueous electrolyte solution resulted in capacity of 130 mAh g−1 and exceptional capacity retention of 99% after 1000 cycles. Although the concept of active current collectors needs to be refined before it can be implemented in commercial cells, our findings indicate that this approach could be useful for improving overall cell performance without requiring significant changes to its configuration.

We demonstrate a novel surface modification of Li- and Mn-rich cathode materials 0.33Li

Out of the many challenges in the realization of lithium–O2 batteries (LOB), the major is to deal with the instability of the electrolyte and the cathode interface under the stringent environment of both oxygen reduction and evolution reactions. Lithium nitrate was recently proposed as a promising salt for LOB because of its capability to stabilize the lithium anode by the formation of a solid electrolyte interphase, its low level of dissociation in aprotic solvents, and its catalytic effect toward oxygen evolution reaction (OER) in rechargeable LOB. Nevertheless, a deeper understanding of the influence of nitrate on the stability and electrochemical response of the cathode in LOB is yet to be realized. Additionally, it is well accepted that carbon instability toward oxidation is a major reason for early failure of LOB cells; therefore, it is essential to investigate the effect of electrolyte components on this side of the battery. In the present work, we show that nitrate leads to interfacial changes, wh...

Most of the recently discovered layered materials such as MoS2 or MoSe2 are n-type, while few materials, such as phosphorene, which suffers from rapid oxidation, are p-type. To form devices such as p–n junctions and heterojunctions, new p-type mono-/few-layers are needed. Here, we report a one-step synthesis of layered, crystalline, p-type copper sulfide by thermal annealing of a standard copper foil in an inert environment using chemical vapor deposition (CVD). Optical spectroscopies (photoluminescence and absorption) show definite correlating features around 2.5 eV. Surface photovoltage spectroscopy shows a photovoltage reduction around the same energy range, which would be expected from a bandgap of a p-type material, and p-type conductivity was also observed using a thermoelectric probe. TEM, XRD, and AFM showed that the synthesized material is layered and has a unique stoichiometry of Cu9S5. Using sonication and dropcasting, we succeeded to isolate few-layers and monolayers. We observed good bulk ele...

The formation and growth of the Li2O2 discharge product impacts the reversibility of the oxygen evolution and reduction reactions in Li-O2 batteries which may lead to a shorter cycle life. A clear understanding of the surface reactions and the growth mechanism of Li2O2 requires probing dynamic changes on the surface of the positive electrodes in situ during the discharge of a Li-O2 battery. To investigate this, we establish an experimental system by adopting a multi-beam optical sensor (MOS) and developing a custom-made battery cell. First, the accuracy and reliability of the system was demonstrated by analyzing the stress accumulation on the Au negative electrode during Li plating/stripping, and the results were consistent with an earlier single-beam scanning deflectometry report. Then, the Li-O2 battery was discharged in LiNO3 in diglyme electrolyte by applying either linear sweep voltammetry or by applying constant current under an O2 environment. Control experiments in Argon-saturated electrolytes indicate surface stress generation due to charge-induced stress. The stress generation on Au positive electrode is attributed to the formation of Li2O2 reaction products on the Au surface and charge-induced stress.

To mitigate the associated challenges of instability and capacity improvement in Na3 V2 (PO4 )2 F3 (NVPF), rationally designed uniformly distributed hollow spherical NVPF and coating the surface of NVPF with ultrathin (≈2 nm) amorphous TiO2 by atomic layer deposition is demonstrated. The coating facilitates higher mobility of the ion through the cathode electrolyte interphase (CEI) and enables higher capacity during cycling. The TiO2 @NVPF exhibit discharge capacity of >120 mAhg-1 , even at 1C rates, and show lower irreversible capacity in the first cycle. Further, nearly 100% capacity retention after rate performance in high current densities and 99.9% coulombic efficiency after prolonged cycling in high current density is reported. The improved performance in TiO2 @NVPF is ascribed to the passivation behavior of TiO2 coating which protects the surface of NVPF from volume expansion, significantly less formation of carbonates, and decomposition of electrolyte, which is also validated through post cycling analysis. The study shows the importance of ultrathin surface protection artificial CEI for advanced sodium-ion battery cathodes. The protection layer is diminishing parasitic reaction, which eventually enhances the Na ion participation in reaction and stabilizes the cathode structure.