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We demonstrate that the ß-polymorph of zinc dicyanamide, Zn[N(CN)2]2, can be efficiently used as a negative electrode material for lithium-ion batteries. Zn[N(CN)2]2 exhibits an unconventional increased capacity upon cycling with a maximum capacity of about 650 mAh·g-1 after 250 cycles at 0.5C, an increase of almost 250%, and then maintaining a large reversible capacity of more than 600 mAh·g-1 for 150 cycles. Such an increased capacity is primarily attributed to the increased level of activity in the conversion reaction. A combination of conversion-type and alloy-type mechanisms is revealed in this anode material via advanced characterization studies and theoretical calculations. This mechanism, observed here for the first time in transition-metal dicyanamides, is probably responsible for the outstanding electrochemical performance. We believe that this study guides the development of new high-capacity anode materials.

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Due to the unique "Grotthus mechanism", aqueous proton batteries (APBs) are promising energy devices with intrinsic safety and sustainability. Although polymers with tunable molecular structures are ideal electrode materials, their unsatisfactory proton-storage redox behaviors hinder the practical application in APB devices. Herein, a novel planar phenazine (PPHZ) polymer with a robust and extended imine-rich skeleton is synthesized and used for APB application for the first time. The long-range planar configuration achieves ordered molecular stacking and reduced conformational disorder, while the high conjugation with strong π-electron delocalization optimizes energy bandgap and electronic properties, enabling the polymer with low proton diffusion barriers, high redox activity, and superior electron affinity. As such, the PPHZ polymer as an electrode material exhibits fast, stable, and unrivaled proton-storage redox behaviors with a large capacity of 273.3 mAh g-1 at 0.5 A g-1 (1 C) in 1 M H2SO4 electrolyte, which is the highest value among proton-inserted electrodes in aqueous acidic electrolytes. Dynamic in situ techniques confirm the high redox reversibility upon proton uptake/removal, and the corresponding protonation pathways are elucidated by theoretical calculations. Moreover, a pouch-type APB cell using PPHZ electrode exhibits an ultralong lifespan over 30 000 cycles, further verifying its promising application prospect.

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Memristors are used in artificial neural networks owing to their exceptional integration capabilities and scalability. However, traditional memristors are hampered by limited resistance states and randomness, which curtails their application. The migration of metal ions critically influences the number of conductance states and the linearity of weight updates. Semi-metal filaments can provide subquantum conductance changes to the memristors due to the smaller single-atom conductance, such as Sb (≈0.01 G0 = 7.69 × 10-7 S). Here, a memristor featuring an active electrode composed of semi-metal Sb is introduced for the first time. This memristor demonstrates precise conductance control, a large on/off ratio, consistent switching, and prolonged retention exceeding 105 s. Density functional theory (DFT) calculations and characterization methods reveal the formation of Sb filaments during a set process. The interaction between Sb and O within the dielectric layer facilitates the Sb filaments' ability to preserve their morphology in the absence of electric fields.

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Sodium-ion batteries (SIBs) have been extensively studied owing to the abundance and low-price of Na resources. However, the infeasibility of graphite and silicon electrodes in sodium-ion storage makes it urgent to develop high-performance anode materials. Herein, α-MnSe nanorods derived from δ-MnO2 (δ-α-MnSe) are constructed as anodes for SIBs. It is verified that α-MnSe will be transferred into ß-MnSe after the initial Na-ion insertion/extraction, and δ-α-MnSe undergoes typical conversion mechanism using a Mn-ion for charge compensation in the subsequent charge-discharge process. First-principles calculations support that Na-ion migration in defect-free α-MnSe can drive the lattice distortion to phase transition (alpha → beta) in thermodynamics and dynamics. The formed ß-MnSe with robust lattice structure and small Na-ion diffusion barrier boosts great structure stability and electrochemical kinetics. Hence, the δ-α-MnSe electrode contributes excellent rate capability and superior cyclic stability with long lifespan over 1000 cycles and low decay rate of 0.0267% per cycle. Na-ion full batteries with a high energy density of 281.2 Wh·kg-1 and outstanding cyclability demonstrate the applicability of δ-α-MnSe anode.

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For the first time, an electrochemical mechanism of oxidative dissolution of silver nanoparticles in aqueous solutions is suggested and substantiated. The dissolution is caused by the occurrence of two interrelated electrochemical processes: (1) silver oxidation on a microanode and (2) oxygen reduction on a microcathode. According to the suggested model, the standard electrode potential of a nanoparticle decreases with a decrease in its size, which leads to an increase in the electromotive force of the oxidative dissolution of silver. A proportional dependence of the solubility of nanoparticles on their standard potential is revealed. An empirical equation is derived that relates the solubility of AgNPs to their electrode potential and size. In the course of oxidation, silver nanoparticles undergo aggregation with a gradual increase in the potential to the value characteristic of the bulk metal. This leads to the deceleration and practical cessation of the dissolution.

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Mo-based heterostructures offer a new strategy to improve the electronics/ion transport and diffusion kinetics of the anode materials for sodium-ion batteries (SIBs). MoO2/MoS2 hollow nanospheres have been successfully designed via in-situ ion exchange technology with the spherical coordination compound Mo-glycerates (MoG). The structural evolution processes of pure MoO2, MoO2/MoS2, and pure MoS2 materials have been investigated, illustrating that the structureofthenanospherecan be maintained by introducing the S-Mo-S bond. Based on the high conductivity of MoO2, the layered structure of MoS2 and the synergistic effect between components, as-obtained MoO2/MoS2 hollow nanospheres display enhanced electrochemical kinetic behaviors for SIBs. The MoO2/MoS2 hollow nanospheres achieve a rate performance with 72% capacity retention at a current of 3200 mA g-1 compared to 100 mA g-1. The capacity can be restored to the initial capacity after a current returns to 100 mA g-1, while the capacity fading of pure MoS2 is up to 24%. Moreover, the MoO2/MoS2 hollow nanospheres also exhibit cycling stability, maintaining a stable capacity of 455.4 mAh g-1 after 100 cycles at a current of 100 mA g-1. In this work, the design strategy for the hollow composite structure provides insight into the preparation of energy storage materials.

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Given the high energy density and eco-friendly characteristics, lithium-carbon dioxide (Li-CO2) batteries have been considered to be a next-generation energy technology to promote carbon neutral and space exploration. However, Li-CO2 batteries suffer from sluggish reaction kinetics, causing large overpotential and poor energy efficiency. Here, we observe enhanced reaction kinetics in aprotic Li-CO2 batteries with unconventional phase 4H/face-centered cubic (fcc) iridium (Ir) nanostructures grown on gold template. Significantly, 4H/fcc Ir exhibits superior electrochemical performance over fcc Ir in facilitating the round-trip reaction kinetics of Li+-mediated CO2 reduction and evolution, achieving a low charge plateau below 3.61 V and high energy efficiency of 83.8%. Ex situ/in situ studies and theoretical calculations reveal that the boosted reaction kinetics arises from the highly reversible generation of amorphous/low-crystalline discharge products on 4H/fcc Ir via the Ir-O coupling. The demonstration of flexible Li-CO2 pouch cells with 4H/fcc Ir suggests the feasibility of using unconventional phase nanomaterials in practical scenarios.

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Electrochemical mechanisms of molten salt electrolysis from TiO2 to titanium were investigated by Potentiostatic electrolysis, cyclic voltammetry, and square wave voltammetry in NaCl-CaCl2 at 800 °C. The composition and morphology of the product obtained at different electrolysis times were characterized by XRD and SEM. CaTiO3 phase was found in the TiO2 electrochemical reduction process. Electrochemical reduction of TiO2 to titanium is a four-step reduction process, which can be summarized as TiO2→Ti4O7→Ti2O3→TiO→Ti. Spontaneous and electrochemical reactions take place simultaneously in the reduction process. The electrochemical reduction of TiO2→Ti4O7→Ti2O3→TiO affected by diffusion was irreversible.

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Open-framework structured materials such as Prussian blue analogues and sodium superionic conductor (NASICON) materials have been regarded as promising electrode candidates for aqueous batteries. These materials exhibit outstanding long cycle stability and high rate capacity retention, due to their high ion diffusive rate in the crystal and the stable structure maintenance in the electrochemical reaction process. Herein, an open-framework structured material [Ni(en)2]3[Fe(CN)6]2 (NienHCF) is prepared and first used as a cathode material for aqueous sodium- and potassium-ion batteries. The resultant material exhibits a high output potential and outstanding cycle performance (93.4% after 500 cycles at 1 A g-1) in K-ion batteries. Meanwhile, the electrochemical reaction mechanism is investigated. After coupling with the activated carbon anode, the K-ion full cell has 91.5% capacity retention at 5 A g-1 and retains 77.2% after 1000 cycles at 0.5 A g-1, exhibiting the potential as an electrode material for rechargeable aqueous K-ion and Na-ion batteries.

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Careful development and optimization of negative electrode (anode) materials for Na-ion batteries (SIBs) are essential, for their widespread applications requiring a long-term cycling stability. BiFeO3 (BFO) with a LiNbO3-type structure (space group R3c) is an ideal negative electrode model system as it delivers a high specific capacity (770 mAh g-1), which is proposed through a conversion and alloying mechanism. In this work, BFO is synthesized via a sol-gel method and investigated as a conversion-type anode model-system for sodium-ion half-cells. As there is a difference in the first and second cycle profiles in the cyclic voltammogram, the operating mechanism of charge-discharge is elucidated using in operando X-ray absorption spectroscopy. In the first discharge, Bi is found to contribute toward the electrochemical activity through a conversion mechanism (Bi3+ → Bi0), followed by the formation of Na-Bi intermetallic compounds. Evidence for involvement of Fe in the charge storage mechanism through conversion of the oxide (Fe3+) form to metallic Fe and back during discharging/charging is also obtained, which is absent in previous literature reports. Reversible dealloying and subsequent oxidation of Bi and oxidation of Fe are observed in the following charge cycle. In the second discharge cycle, a reduction of Bi and Fe oxides is observed. Changes in the oxidation states of Bi and Fe, and the local coordination changes during electrochemical cycling are discussed in detail. Furthermore, the optimization of cycling stability of BFO is carried out by varying binders and electrolyte compositions. Based on that, electrodes prepared with the Na-carboxymethyl cellulose (CMC) binder are chosen for optimization of the electrolyte composition. BFO-CMC electrodes exhibit the best electrochemical performance in electrolytes containing fluoroethylene carbonate (FEC) as the additive. BFO-CMC electrodes deliver initial capacity values of 635 and 453 mAh g-1 in the Na-insertion (discharge) and deinsertion (charge) processes, respectively, in the electrolyte composition of 1 M NaPF6 in EC/DEC (1:1, v/v) with a 2% FEC additive. The capacity values stabilize around 10th cycle and capacity retention of 73% is observed after 60 cycles with respect to the 10th cycle charge capacity.

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Rechargeable aqueous zinc-manganese oxide batteries have attracted extensive attention in energy-storage systems owing to their high safety and low cost but still suffer from the lack of advanced cathode materials with both high capacity and a long cycle life. Here, the bismuth-doped α-MnO2 was synthesized by a hydrothermal method. The preintercalation of Bi3+ effectively enlarges the lattice spacing and boosts the electrochemical performance of Zn/MnO2 batteries. The systematical studies suggest that Bi doping significantly optimized the electrochemical behavior and especially enhanced the reversibility of dissolution-deposition and phase transition processes. As a result, the Bi-doped α-MnO2 cathode achieves a superior performance: high reversible specific capacity (325 mA h g-1 at 300 mA g-1) and long cycling stability (90.9% capacity retention after 2000 cycles at 1000 mA g-1). By comparison with the α-MnO2 electrode, the Bi-doped α-MnO2 electrode exhibits a longer and stabler discharge plateau. It is different from most anionic doping methods, which attribute the performance improvement to superior ion diffusion kinetics and enhanced structural stability. Therefore, this work offers a new viewpoint and approach to improve the electrochemical property of Zn/MnO2 batteries.

RESUMEN

To date, elemental sulfur has been considered as a prospective cathode material for exploring high-energy power systems with low cost and sustainability. However, its practical commercialization has been impeded by inherent drawbacks of notorious capacity decay, unsatisfied insulating nature, and sluggish conversion chemistry. To address these issues, for the first time, freestanding nanofibrous networks with hierarchical nanostructures are facilely constructed by inlaying electrocatalytic bimetallic chalcogenides (FexMn1-xS nanoparticles) into conductive graphene nanosheet (GN)-doped sulfurized polyacrylonitrile (SPAN) fiber matrices. Covalent-bonded SPAN featuring an insoluble mechanism serves as a reliable cathode substrate with enhanced electrostability and high sulfur utilization, while high-surface-area GN dopants promote conductivity improvement and rapid electron transfer. Meanwhile, the results prove that sulfiphilic FexMn1-xS nanoparticles with abundant electrochemically active sites facilitate construction of uniform deposition interfaces and efficient electrocatalysis conversion toward lithium polysufides. This feasible catalytic-insoluble cathode strategy drives the Li-S battery, which exhibits excellent electrochemical performances with a remarkable reversible discharge capacity of 967 mA h g-1 and a capacity retention of 623 mA h g-1 after 500 cycles. Moreover, the corresponding lithiation/delithiation mechanisms are systematically investigated through complementary morphological and spectral analyses, providing valuable insights into advanced metal-sulfur batteries.

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Ammonium vanadate with bronze structure (NH4V4O10) is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost. However, the extraction of [Formula: see text] at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation. In this work, partial [Formula: see text] ions were pre-removed from NH4V4O10 through heat treatment; NH4V4O10 nanosheets were directly grown on carbon cloth through hydrothermal method. Deficient NH4V4O10 (denoted as NVO), with enlarged interlayer spacing, facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure. The NVO nanosheets delivered a high specific capacity of 457 mAh g-1 at a current density of 100 mA g-1 and a capacity retention of 81% over 1000 cycles at 2 A g-1. The initial Coulombic efficiency of NVO could reach up to 97% compared to 85% of NH4V4O10 and maintain almost 100% during cycling, indicating the high reaction reversibility in NVO electrode.

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Sodium-selenium (Na-Se) batteries have aroused enormous attention due to the large abundance of the element sodium as well as the high electronic conductivity and volumetric capacity of selenium. In this battery system, some primary advances in electrode materials have been achieved, mainly involving the design of Se-based cathode materials. In this Review, the electrochemical mechanism is discussed, thus revealing the main challenges in Na-Se batteries. Then, the advances in the design of Se-based cathode materials for Na-ion storage are systemically summarized, classified, and discussed, including Se/carbon composite, Se/polar material/carbon composites, and hybrid SexSy alloys. Some potential strategies enabling the improvement of crucial challenges and enhancement of electrochemical performance are also proposed to provide guidelines for the enhancements of Na-ion storage. An outlook for future valuable research directions is proposed to understand more deeply the electrochemical mechanism of Na-Se batteries and promote their further developments in full cell performance and commercialization.

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Up to now, the silicon-graphite anode materials with commercial prospect for lithium batteries (LIBs) still face three dilemmas of the huge volume effect, the poor interface compatibility, and the high resistance. To address the above challenges, micro-nano structured composites of graphite coating by ZnO-incorporated and carbon-coated silicon (marked as Gr@ZnO-Si-C) are reasonably synthesized via an efficient and convenient method of liquid phase self-assembly synthesis combined with annealing treatment. The designed composites of Gr@ZnO-Si-C deliver excellent lithium battery performance with good rate performance and stable long-cycling life of 1000 cycles with reversible capacities of 1150 and 780 mAh g-1 tested at 600 and 1200 mA g-1 , respectively. The obtained results reveal that the incorporated ZnO effectively improve the interface compatibility between electrolyte and active materials, and boost the formation of compact and stable surface solid electrolyte interphase layer for electrodes. Furthermore, the pyrolytic carbon layer formed from polyacrylamide can directly improve electrical conductivity, decrease polarization, and thus promote their electrochemical performance. Finally, based on the scalable preparation of Gr@ZnO-Si-C composites, the pouch full cells of Gr@ZnO-Si-C||NCM523 are assembled and used to evaluate the commercial prospects of Si-graphite composites, offering highly useful information for researchers working in the battery industry.

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Midazolam (MID) is a sedative drug which can be added in beverage samples as drug-facilitated-sexual assault (date rape drug). This type of drug has short half-life in biological fluids (not detectable) which often prevents the correlation between drug abuse and crime. In this work, we described a simple and low-cost method for fast screening and selective determination of MID in beverage samples (vodka, whiskey and red wine). For the first time, the electrochemical oxidation of MID was used for this purpose. The oxidation mechanism was studied using electrochemical techniques (cyclic and square-wave voltammetry) and computational simulations (density functional theory calculations). Differential-pulse voltammetry, boron-doped diamond electrode (BDDE), and Britton-Robinson (BR) buffer (pH = 2) were selected as electrochemical analysis technique, working electrode and supporting electrolyte, respectively. Different linear response ranges (4-25 µmol L-1 with r = 0.9972; 1-10 µmol L-1 with r = 0.9951; 1-15 µmol L-1 with r = 0.9982) and limits of detection (0.46, 0.43 and 0.33 µmol L-1) were obtained for the analysis of vodka, whisky, and red wine solutions, respectively. The precision and accuracy were satisfactory considering the low relative standard deviation values (RSD < 6.3%, n = 15) and minimal sample matrix effects (recovery values between 87 and 103%).

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For Si anode materials used for lithium ion batteries (LIBs), developing an effective solution to overcome their drawbacks of large volume change and poor electronic conductivity is highly desirable. Here, the composites of ZnO-incorporated and carbon-coated silicon/porous-carbon nanofibers (ZnO-Si@C-PCNFs) are designed and synthesized via a traditional electrospinning method. The prepared ZnO-Si@C-PCNFs can obviously overcome these two drawbacks and provide excellent LIB performance with excellent rate capability and stable long cycling life of 1000 cycles with reversible capacity of 1050 mA h g-1 at 800 mA g-1 . Meanwhile, anodes of ZnO-Si@C-PCNFs attached with Ag particles display enhanced LIB performance, maintaining an average capacity of 920 mA h g-1 at a large current of 1800 mA g-1 even for 1000 cycles with negligible capacity loss and excellent reversibility. In addition, the assembling method with important practical significance for a simple pouch full cell is designed and used to evaluate the active materials. The Ag/ZnO-Si@C-PCNFs are prelithiated and assembled in full cells using LiNi0.5 Co0.2 Mn0.3 O2 (NCM523) as cathodes, exhibiting higher energy density (230 W h kg-1 ) of 18% than that of 195 W h kg-1 for commercial graphite//NCM523 full pouch cells. Importantly, the comprehensive mechanisms of enhanced electrochemical kinetics originating from ZnO-incorporation and Ag-attachment are revealed in detail.

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Xanthine oxidase (XO) can catalyze xanthine to uric acid and has also been linked with the extension of some serious diseases such as cancer, gout, diabetes and so on. Thymol is a part of diet in the form of spices. Due to the high antioxidant activity, its inhibitory effect on XO was studied in the present work. XO organized in four redox domains which exhibiting electrochemical signals. Therefore, voltammetric methods can be used to obtain the valuable information about the action mechanism of thymol on XO. However, there are extreme complexities in these biological sample matrices which make the deeper understanding of inhibition mechanism of thymol on XO activity is difficult. Thus, development of electrochemical techniques coupled with the four-way parallel factor analysis (PARAFAC) has provided promising solutions for analyzing of complex matrix. To better explore this inhibitory effect, electrochemical technologies have been used as a complement with ultraviolet and visible (UV-Vis) spectroscopy and molecular docking studies. For the first time, molecular docking studies were used to gain a fundamental understanding to explain how the electron transfer coupling occurs at XO active sites in the presence of thymol. It is in good agreement with the experimental data. These studies reveal that thymol could enter into the catalytic centers of XO. Also, it inhibits the XO activity through the direct binding to flavin adenine dinucleotides (FAD) center. The results display dose-dependent inhibition of XO with thymol. Its inhibitory activity was linked to its antioxidant properties to reduce the formation of free radicals (FRs) and related diseases.

Asunto(s)

RESUMEN

The development of self-standing and binder-free O2 electrodes is significant for enhancing the total specific energy density and suppressing parasitic reactions for Li-O2 batteries, which is still a formidable challenge thus far. Here, a three-dimensional foam-like composite composed of Mo2C nanorods decorated by different amounts of N-doped carbon (Mo2C-NR@xNC (x = 5, 11, and 16 wt %)) was directly employed as the O2 electrode without applications of any binders and current collectors. Mo2C-NR@xNC presents a network microstructure with interconnected macropore and mesoporous channels, which is beneficial to achieving fast Li+ migration and O2 diffusion, facilitating the electrolyte impregnation, and providing enough space for Li2O2 storage. Additionally, the coated N-doped carbon layer can largely improve the electrochemical stability and conductivity of Mo2C. The cell with Mo2C-NR@11NC shows a considerable cyclability of 200 cycles with an overpotential of 0.28 V in the first cycle at a constant current density of 100 mA g-1, a superior reversibility associated with the formation and decomposition of Li2O2 as desired, and a high electrochemical stability. On the basis of the experimental results, the electrochemical mechanism for the cell using Mo2C-NR@11NC is proposed. These results represent a promising process in the development of a self-standing and binder-free foam-based electrode for Li-O2 batteries.

RESUMEN

Tin was electrodeposited from chloride solutions using a membrane cell under ultrasonic waves. Cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CHR), and chronopotentiometry were applied to investigate the electrochemical mechanism of tin electrodeposition under ultrasonic field. Chronoamperometry curves showed that the initial process of tin electrodeposition followed the diffusion controlled three-dimensional nucleation and grain growth mechanism. The analysis of the cyclic voltammetry and linear sweep voltammetry diagrams showed that the application of ultrasound can change the tin membrane electro-deposition reaction from diffusion to electrochemical control, and the optimum parameters for tin electrodeposition were H+ concentration 3.5 mol·L-1, temperature 35 °C and ultrasonic power 100 W. The coupling ultrasonic field played a role in refining the grain in this process. The growth of tin crystals showed no orientation preferential, and the tin deposition showed a tendency to form a regular network structure after ultrasonic coupling. While in the absence of ultrasonic coupling, the growth of tin crystals has a high preferential orientation, and the tin deposition showed a tendency to form tin whiskers. Ultrasonic coupling was more favorable for obtaining a more compact and smoother cathode tin layer.